Biscyclopentadienyldiene complex containing addition polymerization catalysts

ABSTRACT

Catalysts for polymerizing olefins, diolefins and/or acetylenically unsaturated monomers comprising biscyclopentadienyl, Group 4 transition metal complexes formed with conjugated dienes wherein the diene is bound to the transition metal either in the form of a σ-complex or a π-complex in combination with a cocatalyst or subjected to bulk electrolysis in the presence of compatible, inert non-coordinating anions.

CROSS-REFERENCE TO RELATED APPLICATION

This is a division of the application titled BISCYCLOPENTADIENYL DIENECOMPLEXES by Francis J. Timmers, David D. Devore, James C. Stevens,Robert K. Rosen, Jason Patton, and David Neithamer, U.S. Ser. No.08/481,791, pending, filed Jun. 7, 1995, which is a continuation-in-partof application Ser. No. 08/284,925 filed Aug. 2, 1994, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to certain biscyclopentadienyl Group 4 transitionmetal complexes possessing diene ligands and to polymerization catalystsobtained from such. In one form this invention relates tobiscyclopentadienyl and substituted bis(cyclopentadienyl)titanium,zirconium or hafnium complexes possessing diene ligands in which themetal is either in the +2 or +4 formal oxidation state which can beactivated to form catalysts for the polymerization of olefins and tomethods for preparing such complexes and catalysts.

The preparation and characterization of certain biscyclopentadienyl(Cp₂) zirconium and hafnium diene complexes is described in thefollowing references: Yasuda, et al., Organometallics, 1982, 1, 388(Yasuda I); Yasuda, et al. Acc. Chem. Res., 1985, 18 120 (Yasuda II);Erker, et al., Adv. Organomet. Chem., 1985, 24, 1 (Erker I); Erker etal. Chem. Ber., 1994, 127, 805 (Erker II); and U.S. Pat. No. 5,198,401.The last reference describes the use of Cp₂ Zr(diene) where the Zr is inthe +4 formal oxidation state as an olefin polymerization catalyst incombination with ammonium borate cocatalysts.

Biscyclopentadienyl Group 4 transition metal complexes in which themetal is in the +4 formal oxidation state, and olefin polymerizationcatalysts formed from such complexes by combination with an activatingagent, e.g., alumoxane or ammonium borate, are known in the art. Thus,U.S. Pat. No. 3,242,099 describes the formation of olefin polymerizationcatalysts by the combination of biscyclopentadienyl metal dihalides withalumoxane. U.S. Pat. No. 5,198,401 discloses tetravalentbiscyclopentadienyl Group 4 transition metal complexes and olefinpolymerization catalysts obtained by converting such complexes intocationic form in combination with a non-coordinating anion. Particularlypreferred catalysts are obtained by the combination of ammonium boratesalts with the biscyclopentadienyl titanium, zirconium or hafniumcomplexes. Among the many suitable complexes disclosed arebis(cyclopentadienyl)zirconium complexes containing a diene ligandattached to the transition metal through σ-bonds where the transitionmetal is in its highest (+4) formal oxidation state.

Copending applications, Ser. No. 08/082,197 filed Jun. 24, 1993, (nowabandoned) Ser. No. 08/230,051 filed Apr. 19, 1994 (now abandoned) andSer. No. 08/241,523 filed May 12, 1994 (now U.S. Pat. No. 5,470,993)disclose monocyclopentadienyl diene complexes with titanium or zirconiumin which the metal is in the +2 formal oxidation state and the formationof olefin polymerization catalysts from such complexes by thecombination of the complex with activator compounds such as alumoxane,ammonium borate salts or strong Lewis acids such astris(pentafluorophenyl)borane capable of converting the complexes toactive forms.

The present invention provides novel olefin polymerization catalystswhich can be employed over a wide range of physical conditions and witha wide range of olefin monomers and combinations of such monomers, thusproviding an outstanding opportunity of tailor making polyolefins havingspecifically desired properties.

SUMMARY OF THE INVENTION

The present invention relates to metal complexes containing twocyclopentadienyl groups or substituted cyclopentadienyl groups, saidcomplex corresponding to the formula:

    CpCp'MD

wherein:

M is titanium, zirconium or hafnium in the +2 or +4 formal oxidationstate;

Cp and Cp' are each substituted or unsubstituted cyclopentadienyl groupsbound in an η⁵ bonding mode to the metal, said substitutedcyclopentadienyl group being substituted with from one to fivesubstituents independently selected from the group consisting ofhydrocarbyl, silyl, germyl, halo, cyano, hydrocarbyloxy, and mixturesthereof, said substituent having up to 20 nonhydrogen atoms, oroptionally, two such substituents (except cyano or halo) together causeCp or Cp' to have a fused ring structure, or wherein one substituent onCp and Cp' forms a linking moiety joining Cp and Cp';

D is a stable, conjugated diene, optionally substituted with one or morehydrocarbyl groups, silyl groups, hydrocarbylsilyl groups,silylhydrocarbyl groups, or mixtures thereof, said D having from 4 up to40 nonhydrogen atoms and forming a π-complex with M when M is in the +2formal oxidation state, and forming a σ-complex with M when M is in the+4 formal oxidation state. In the diene complexes in which M is in the+2 formal oxidation state, the diene is associated with M as a π-complexin which the diene normally assumes an s-trans configuration or an s-cisconfiguration in which the bond lengths between M and the four carbonatoms of the conjugated diene are nearly equal (Δd as defined hereafter≧-0.15 Å) whereas in the complexes in which M is in the +4 formaloxidation state, the diene is associated with the transition metal as aσ-complex in which the diene normally assumes a s-cis configuration inwhich the bond lengths between M and the four carbon atoms of theconjugated diene are significantly different (Δd <-0.15 Å). Theformation of the complex with M in either the +2 or +4 formal oxidationstate depends on the choice of the diene, the specific metal complex andthe reaction conditions employed in the preparation of the complex. Thecomplexes wherein the diene is π-bound and M is in the +2 formaloxidation state constitute the preferred complexes of the presentinvention.

The present invention also relates to novel methods of preparing theCpCp'MD complexes involving the reaction of the biscyclopentadienyldihydrocarbyl, dihydrocarbyloxy, dihalide or diamide Group 4 metalcomplexes wherein the metal is in the +4 or +3 formal oxidation state,with a diene, D, and a reducing agent. The use of a reducing agent isoptional when starting with biscyclopentadienyl dihydrocarbyl complexes.

Stated more particularly, the diene metal complexes of the presentinvention may be formed by reacting in any order the followingcomponents:

1) a complex of the formula:

    CpCp'M*X or CpCp'M**X.sub.2

wherein;

Cp and Cp' are as previously defined;

M* is titanium, zirconium or hafnium in the +3 formal oxidation state;

M** is titanium, zirconium or hafnium in the +4 formal oxidation state;and

X is a C₁₋₆ hydrocarbyl, halide, C₁₋₆ hydrocarbyloxy or diC₁₋₆hydrocarbylamide group;

2) a diene corresponding to the formula, D; and

3) optionally when X is C₁₋₆ hydrocarbyl, otherwise, not optionally, areducing agent.

Uniquely, the process when used with diastereomeric mixtures of rac andmeso isomers of metallocenes, can result in formation of only the racdiene metal complex.

Further according to the present invention there are provided catalystsfor polymerization of addition polymerizable monomers comprising acombination of one or more of the above metal complexes and one or oreactivating cocatalysts. The metal complexes wherein the metal is in the+2 formal oxidation state are preferred in the formation of the novelcatalysts of this invention.

Finally according to the present invention there is provided apolymerization process comprising contacting one or more additionpolymerizable monomers and particularly one or more α-olefins with acatalyst comprising one or more of the above metal complexes and one ormore activating cocatalysts.

Generally speaking, the present diene containing complexes are moresoluble in hydrocarbon solvents compared to the corresponding dihalidecomplexes and they are more stable to reductive elimination and otherside reactions than are the corresponding dihydrocarbyl complexes.Catalyst systems comprising such diene containing complexes areaccordingly better adapted to commercial use than are such alternativesystems.

DETAILED DESCRIPTION

All reference to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 1989. Also, any reference to a Group or Groups shall be tothe Group or Groups as reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups.

Useful dienes, D, are dienes that do not decompose under reactionconditions used to prepare the complexes of the invention. Undersubsequent polymerization conditions, or in the formation of catalyticderivatives of the present complexes, the diene group, D, may undergochemical reaction or be replaced by another ligand.

The complexes of the present invention wherein M is in the +2 formaloxidation state contain a neutral diene ligand which is coordinated viaπ-complexation through the diene double bonds, and not through ametallocycle containing σ-bonds. The nature of the diene bond to themetal is readily determined by X-ray crystallography or by NMR spectralcharacterization according to the techniques of Yasuda I, Yasuda II, andErker I, supra, as well as the references cited therein. By the term"π-complex" is meant both the donation and back acceptance of electrondensity by the ligand are accomplished using ligand π-orbitals, i.e.,the diene is π-bound (π-bound diene).

Encompassed within the scope of the present invention also are complexescontaining a diene ligand which is coordinated formally as ametallocycle containing σ-bonds (σ-bound diene) where the metal is inthe +4 formal oxidation state. Such Group 4 metal σ-bound dienecomplexes have a structure which is formally a metallocyclopentenewherein the bonding between the metal and the diene (depicted asstructure i) can be described as a divalent 2-butene-1,4-diyl σ-bondedto a tetravalent metal, optionally containing a single π-bond involvingthe π electrons between internal carbons of the conjugated diene. Suchstructures are depicted as structure ii and structure iii as follows:##STR1##

The nomenclature for such σ-bound diene complexes can be either as ametallocyclopentene (referring to the compounds as 2-butene-1,4-diylcompounds) or generically as the parent diene, i.e., butadiene. Those ofskill in the art will recognize the interchangability of these names.For example, the prior art biscyclopentadienyl zirconium complexcontaining a σ-bound 2,3-dimethyl-1,3-butadiene group would be namedeither bis-cyclopentadienyl 2-butene-2,3-dimethyl-1,4-diyl zirconium orbis-cyclopentadienyl 2,3-dimethyl-1,3-butadiene zirconium.

A suitable method of determining the existence of a π- or σ-complex inconjugated diene containing metal complexes is the measurement ofmetal-carbon atomic spacings for the four carbons of the conjugateddiene using common X-ray crystal analysis techniques. Measurements ofatomic spacings between the metal and C1, C2, C3, and C4 (M-C1, M-C2,M-C3, M-C4, respectively) (where C1 and C4 are the terminal carbons ofthe 4 carbon conjugated diene group and C2 and C3 are the internalcarbons of the 4 carbon conjugated diene group) may be made. If thedifference between these bond distances, Δd, using the followingformula: ##EQU1## is greater than or equal to -0.15 Å, the diene isconsidered to form a π-complex with M and M is formally in the +2oxidation state. If Δd is less than -0.15 Å, the diene is considered toform a σ-complex with M and M is formally in the +4 oxidation state.

Examples wherein the above method for determination of π-complexes hasbeen applied to prior art compounds are found in Erker, et al., Angew.Chem, Int. Ed. Eng., 1984, 23, 455-456 (Erker III) and Yamamoto, et al,Organometallics, 1989, 8, 105-119. In the former reference (η³-allyl)(η⁴ -butadiene)(η⁵ -cyclopentadienyl)zirconium wascrystallographically characterized. The M-C1 and M-C4 distances wereboth 2.360 (±0.005) Å. The M-C2 and M-C3 distances were both 2.463(±0.005) Å, giving a Δd of -0.103 Å. In the latter reference (η⁵-pentamethylcyclopentadienyl)(η⁴ -1,4-diphenyl-1,3-butadiene)titaniumchloride was shown to have M-C1 and M-C4 distances of 2.233 (±0.006) Å.The M-C2 and M-C3 distances were both 2.293 (±0.005) Å, giving a Δd of-0.060 Å. Accordingly, these two complexes contain π-bound diene ligandsand the metal of each is in the +2 formal oxidation state. Erker I alsodisclosed bis(cyclopentadienyl)zirconium (2,3-dimethyl-1,3-butadiene).In this complex the M-C1 and M-C4 distances were 2.300 Å. The M-C2 andM-C3 distances were both 2.597 Å, giving a Δd of -0.297 5<. Accordingly,this complex contains a σ-bound diene and the zirconium is in the +4formal oxidation state. In the use of such X-ray crystal analysistechniques at least "good" and preferably "excellent" determinationquality as defined by G. Stout et al., X-ray Structure Determination, APractical Guide, MacMillan Co., pp. 430-431 (1968) is used.

Alternatively, complexes of the present invention wherein X is aconjugated diene in the form of a π-complex and M is in the +2 formaloxidation state are identified using nuclear magnetic resonancespectroscopy techniques. The teachings of Erker, I to III, supra, C.Kruger, et al. Organometallics, 4, 215-223, (1985), and Yasuda I, supra,disclose these well known techniques for distinguishing between π-boundcomplexes and metallocyclic coordination or σ-bound diene complexes. Theteachings of the foregoing references related to π-bound and σ-bounddiene complexes is hereby incorporated by reference.

It is to be understood that the present complexes may be formed andutilized as a mixture of the π-complexed and σ-complexed diene compoundswhere the metal centers are in the +2 or +4 formal oxidation state.Preferably the complex in the +2 formal oxidation state is present in amolar amount from 0.1 to 100.0 percent, more preferably in a molaramount from 10 to 100.0 percent, most preferably in a molar amount from60 to 100.0 percent. Techniques for separation and purification of thecomplex in the +2 formal oxidation state from the foregoing mixtures areknown in the art and disclosed for example in the previously mentionedYasuda, I, supra, and Erker, I to III, supra, references and may beemployed if desired to prepare and isolate the complexes in greaterpurity.

The metal complexes used to form the diene complexes of the presentinvention are the bis(cyclopentadienyl) dihalides, dihydrocarbyls,diamides and dialkoxides which have heretofore been employed in theformation of metallocene complexes, or which are readily prepared usingwell known synthetic techniques. An extensive list ofbiscyclopentadienyl complexes is disclosed in U.S. Pat. No. 5,198,401which is hereby incorporated by reference.

Preferred complexes of the present invention correspond to the formula:##STR2## wherein:

M is titanium, zirconium or hafnium, preferably zirconium or hafnium, inthe +2 or +4 formal oxidation state;

R' and R" in each occurrence are independently selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R' and R" having up to 20 non-hydrogen atomseach, or adjacent R' groups and/or adjacent R" groups (when R' and R"are not hydrogen, halo or cyano) together form a divalent derivative(i.e., a hydrocarbadiyl, siladiyl or germadiyl group) or one R' and oneR" together (when R' and R" groups are not hydrogen halo or cyano)combine to form a divalent radical (i.e., a hydrocarbadiyl, germadiyl orsiladiyl group) linking the two substituted cyclopentadienyl groups; and

D is a conjugated diene having from 4 to 30 non-hydrogen atoms, whichforms a π-complex with M when M is in the +2 formal oxidation state anda σ-complex with M when M is in the +4 formal oxidation state.

Preferably, R' and R" independently in each ccurrence are selected fromthe group consisting of ydrogen, methyl, ethyl, and all isomers ofpropyl, utyl, pentyl and hexyl, as well as cyclopentyl, cyclohexyl,norbornyl, benzyl, and trimethyl silyl, or adjacent R' groups and/oradjacent R" groups on each cyclopentadienyl ring (except hydrogen) arelinked together thereby forming a fused ring system such as an indenyl,2-methyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl, tetrahydroindenyl,fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl group, or one R'and one R" are linked together forming a 1,2-ethanediyl, 2,2-propanediylor dimethylsilanediyl linking group.

Examples of suitable D moieties include: η⁴ -1,4-diphenyl-1,3-butadiene;η⁴ -1,3-pentadiene; η⁴ -1-phenyl-1,3-pentadiene; η⁴-1,4-dibenzyl-1,3-butadiene; η⁴ -2,4-hexadiene; η⁴-3-methyl-1,3-pentadiene; η⁴ -1,4-ditolyl-1,3-butadiene; η⁴-1,4-bis(trimethylsilyl)-1,3-butadiene, 2,3 dimethyl butadiene,isoprene. Of the foregoing 1,4-diphenyl-1,3-butadiene,1-phenyl-1,3-pentadiene, and 2,4 hexadiene, i.e, the terminally di-C₁₋₁₀hydrocarbyl substituted 1,3-dienes generally form π-complexes, whereasthe solely internally C₁₋₁₀ hydrocarbyl substituted 1,3-dienes, such asisoprene or 2,3-dimethyl butadiene generally form σ-complexes. Preferreddienes are terminally C₁₋₁₀ hydrocarbyl substituted 1,3-butadienes.2,4-hexadiene, 1-phenyl-1,3-pentadiene, 1,4-diphenylbutadiene or1,4-ditolylbutadiene

Examples of the above metal complexes where the metal is titanium,zirconium or hafnium and preferably zirconium or hafnium include: bis(η⁵-cyclopentadienyl)-zirconium s-trans(η⁴ -1,4-trans,trans-diphenyl-1,3-butadiene), bis(cyclopentadienyl)zirconiums-cis(2,3-dimethyl-1,3-butadiene), (bis-η⁵ -cyclopentadienyl)zirconiumη⁴ -1,4-ditolyl-1,3-butadiene, bis(η⁵ -cyclopentadienyl)zirconium η⁴-2,4-hexadiene, bis(η⁵ -cyclopentadienyl)zirconium η⁴-3-methyl-1,3-pentadiene, bis(η⁵ --cyclopentadienyl)zirconium η⁴-1-phenyl-1,3-pentadiene, bis(pentamethyl-η⁵ -cyclopentadienyl)zirconiumη⁴ -1,4--diphenyl-1,3-butadiene, bis(pentamethyl-η⁵-cyclopentadienyl)zirconium η⁴ -1,4-dibenzyl-1,3-butadiene,bis(pentamethyl-η⁵ -cyclopentadienyl)zirconium η⁴ -2,4-hexadiene,bis(pentamethyl-η⁵ -cyclopentadienyl)zirconium η⁴-3-methyl-1,3-pentadiene, bis(ethyltetramethyl-η⁵-cyclopentadienyl)zirconium η⁴ -1,4-diphenyl-1,3-butadiene,bis(ethyltetramethyl-η⁵ -cyclopentadienyl)-zirconium η⁴-1,4-dibenzyl-1,3-butadiene, bis(ethyltetramethyl-η⁵-cyclopentadienyl)zirconium η⁴ -2,4-hexadiene, bis(ethyltetramethyl-η⁵-cyclopentadienyl)zirconium η⁴ -3-methyl-1,3-pentadiene, (pentamethyl-η⁵-cyclopentadienyl), (η⁵ -cyclopentadienyl)zirconium η⁴-1,4-dibenzyl-1,3-butadiene, (pentamethyl-η⁵ -cyclopentadienyl), (η⁵-cyclopentadienyl)zirconium η⁴ -2,4-hexadiene, bis(t-butyl-η⁵-cyclopentadienyl)-1,2-zirconium η⁴ -1,4-diphenyl-1,3-butadiene,bis(t-butyl-η⁵ -cyclopentadienyl)zirconium η⁴-1,4-dibenzyl-1,3-butadiene, bis(t-butyltetramethyl-η⁵-cyclopentadienyl)zirconium η⁴ -2,4-hexadiene, η⁵ -cyclopentadienyl,(tetramethyl-η⁵ -cyclopentadienyl)zirconium η⁴ -3-methyl-1,3-pentadiene,bis(pentamethyl-η⁵ -cyclopentadienyl)zirconium η⁴-1,4-diphenyl-1,3-butadiene, bis(pentamethyl-η⁵-cyclopentadienyl)zirconium η⁴ -1-phenyl-1,3-pentadiene,bis-(tetramethyl-η⁵ -cyclopentadienyl)zirconium η⁴-3-methyl-1,3-pentadiene, bis(methyl-η⁵ -cyclopentadienyl)zirconium η⁴-1,4-diphenyl-1,3-butadiene, bis(η⁵ -cyclopentadienyl)zirconium η⁴-1,4-dibenzyl-1,3-butadiene, bis(trimethyl-silyl-η⁵-cyclopettadienyl)zirconium η⁴ -2,4-hexadiene, bis(trimethylsilyl-η⁵-cyclopentadienyl)-zirconium η⁴ -3-methyl-1,3--pentadiene, (η⁵-cyclopentadienyl)(trimethylsilyl-η⁵ -cyclopentadienyl)zirconium η⁴-1,4-diphenyl-1,3-butadiene, (η⁵ -cyclopentadienyl)(trimethylsilyl-η⁵-cyclopentadienyl)zirconium η⁴ -1,4-dibenzyl-1,3-butadiene,(trimethylsilyl-η⁵ -cyclopentadienyl)-(pentamethyl-η⁵-cyclopentadienyl)zirconium η⁴ -2,4-hexadiene, bis(benzyl-η⁵-cyclopentadienyl)zirconium η⁴ -3-methyl-1,3-pentadiene, bis(η⁵-indenyl)-zirconium η⁴ -1,4-diphenyl-1,3-butadiene, bis(η⁵-indenyl)zirconium η⁴ -1,4-dibenzyl-1,3-butadiene,bis(η5-indenyl)zirconium η⁴ -2,4-hexadiene, bis(η⁵ -indenyl)zirconium η⁴-3-methyl-1,3-pentadiene, bis(η⁵ -fluorenyl)zirconium η⁴-1,4-diphenyl-1,3-butadiene, (pentamethylcyclopentadienyl)-(η⁵-fluorenyl)zirconium η⁴ -1-phenyl-1,3-pentadiene, bis(η⁵-fluorenyl)zirconium η⁴ -1,4-dibenzyl-1,3-butadiene, bis(η⁵-fluorenyl)-zirconium η⁴ -2,4-hexadiene, and bis(η⁵ -fluorenyl)zirconiumη⁴ -3-methyl-1,3-pentadiene.

Additional bis-cyclopentadienyl compounds of formula A include thosecontaining a bridging group linking the cyclopentadienyl groups.Preferred bridging groups are those corresponding to the formula(ER'"₂)_(x) wherein E is carbon, silicon or germanium, R'" independentlyeach occurrence is hydrogen or a group selected from silyl, hydrocarbyl,hydrocarbyloxy and combinations thereof, or two R'" groups together forma ring system, said R'" having up to 30 carbon or silicon atoms, and xis an integer from 1 to 8. Preferably R'" independently each occurrenceis methyl, benzyl, tert-butyl or phenyl.

Examples of the foregoing bridged cyclopentadienyl containing complexesare compounds corresponding to the formula: ##STR3##

wherein:

M, D, E, R'" and x are as previously defined, and R' and R" in eachoccurrence are independently selected from the group consisting ofhydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinationsthereof, said R' and R" having up to 20 non-hydrogen atoms each, oradjacent R' groups and/or adjacent R" groups (when R' and R" are nothydrogen, halo or cyano) together form a divalent derivative (i.e., ahydrocarbadiyl, siladiyl or germadiyl group) or one R' and one R"together (when R' and R" groups are not hydrogen halo or cyano) combineto form a divalent radical (i.e., a hydrocarbadiyl, germadiyl orsiladiyl group) linking the two cyclopentadienyl groups.

Such bridged structures are especially suited for the preparation ofpolymers having stereoregular molecular structure. In such capacity itis preferred that the complex be nonsymmetrical or possess a chiral,stereorigid structure. Examples of the first type are compoundspossessing different delocalized n-bonded systems, such as onecyclopentadienyl group and one fluorenyl group. Similar systems based onTi(IV) or Zr(IV) were disclosed for preparation of syndiotactic olefinpolymers in Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256 (1980).Examples of chiral structures include bis-indenyl complexes. Similarsystems based on Ti(IV) or Zr(IV) were disclosed for preparation ofisotactic olefin polymers in Wild et al., J. Organomet. Chem, 232,233-47, (1982).

Exemplary bridged cyclopentadienyl moieties in the complexes of formula(B) are: dimethylsilanediyl-bis((2-methyl-4-phenyl)-1-indenyl)zirconiums-trans(η⁴ -1,4-trans-trans-diphenyl-1,3-butadiene),dimethylsilanediyl-bis((2-methyl-4-(1-napthyl))-1-indenyl)zirconiums-trans(η⁴ -1,4-trans-trans-diphenyl-1,3-butadiene),1,2-ethanediyl-bis(2-methyl-4-(1-phenyl)-1-indenyl)zirconium s-trans(η⁴-1,4-trans-trans-diphenyl-1,3-butadiene),1,2-ethanediyl-bis(2-methyl-4-(1-napthyl)-1-indenyl)zirconium s-trans(η⁴-1,4-trans-trans-diphenyl-1,3-butadiene),[1,2-ethanediylbis(1-indenyl)]zirconium s-trans(η⁴-trans,trans-1,4-diphenyl-1,3-butadiene),[1,2-ethanediylbis(1-tetrahydroindenyl)]-zirconium s-trans(η⁴-trans,trans-1,4-diphenyl-1,3-butadiene),[1,2-ethanediylbis(1-indenyl)]hafnium s-trans(η⁴-trans,trans-1,4-diphenyl-1,3-butadiene), and[2,2-propanediyl(9-fluorenyl)-(cyclopentadienyl)]-zirconium(trans,trans-1,4-diphenyl-1,3-butadiene).

In general, the complexes of the present invention can be prepared bycombining a diene compound, corresponding to the group D in theresulting complex, with a metal complex containing only hydrocarbylleaving groups. Heating the solution, for example use of boilingtoluene, may expedite the reaction. In the event the metal complexcontains hydrocarbyloxy, amide or halogen ligands (and otherwisecontaining the desired structure of the resulting complexes) andoptionally when the metal complex contains only hydrocarbyl leavinggroups, the metal complex, the diene, or the above mixture of metalcomplex and diene, is also contacted with a reducing agent. The processpreferably is conducted in a suitable noninterfering solvent at atemperature from -100° C. to 300° C., preferably from -78 to 130° C.,most preferably from -10 to 120° C. Metal complexes in either the +4 or+3 formal oxidation state may be utilized.

By the term "reducing agent" as used herein is meant a metal or compoundwhich, under reducing conditions can cause the transition metal to bereduced from the +4 or +3 formal oxidation state to the +2 formaloxidation state. The same procedure is employed for the preparation ofthe diene complexes where M is in the +2 formal oxidation state or inthe +4 formal oxidation state, the nature of formal oxidation state of Min the complex being formed being primarily determined by the dieneemployed. Examples of suitable metal reducing agents are alkali metals,alkaline earth metals, aluminum, zinc and alloys of alkali metals oralkaline earth metals such as sodium/mercury amalgam andsodium/potassium alloy. Specific examples of suitable reducing agentcompounds are sodium naphthalenide, potassium graphite, lithium alkyls,aluminum trialkyls and Grignard reagents. Most preferred reducing agentsare the alkali metals or alkaline earth metals, C₁₋₆ alkyl lithium, triC₁₋₆ alkyl aluminum and Grignard reagents, especially lithium, n-butyllithium and triethyl aluminum. The use of a C₁₋₆ alkyl lithium ortriethylaluminum reducing agent is especially preferred.

Highly preferred diene compounds are 1,3-pentadiene;1,4-diphenyl-1,3-butadiene; 1-phenyl-1,3-pentadiene;1,4-dibenzyl-1,3-butadiene; 2,4-hexadiene; 3-methyl-1,3-pentadiene;1,4-ditolyl-1,3-butadiene; and 1,4-bis-(trimethylsilyl)-1,3-butadiene.All geometric isomers of the foregoing diene compounds may be utilized.

Suitable reaction media for the formation of the complexes are aliphaticand aromatic hydrocarbons and halohydrocarbons, ethers, and cyclicethers. Examples include straight and branched-chain hydrocarbons suchas isobutane, butane, pentane, hexane, heptane, octane, and mixturesthereof; cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; aromatic and hydrocarbyl-substituted aromatic compounds such asbenzene, toluene, xylene, and the like, C₁₋₄ dialkyl ethers, C₁₋₄dialkyl ether derivatives of (poly)alkylene glycols, andtetrahydrofuran. Mixtures of the foregoing list of suitable solvents arealso suitable.

The recovery procedure involves separation of the resulting byproductsand devolatilization of the reaction medium. Extraction into a secondarysolvent may be employed if desired. Alternatively, if the desiredproduct is an insoluble precipitate, filtration or other separationtechnique may be employed.

The present inventors have further discovered that ansa-racbiscyclopentadienyl Group 4 metal complexes (where "rac" refers to aracemic mixture of enantiomers) uniquely form stable complexes with theconjugated diene, particularly with a trans, trans-terminallydisubstituted 1,3-butadiene. The corresponding meso-biscyclopentadienylGroup 4 metal diene complexes are less stable and not recoverable,unless extreme care is utilized. Accordingly, this discovery allows theartisan to separate mixtures of diastereomers of biscyclopentadienylGroup 4 metal complexes containing hydrocarbyl, hydrocarbyloxy, halideor amide leaving groups merely by contacting the mixture with a C₄₋₄₀conjugated diene and the reducing agent, where called for, andrecovering the resulting ansa-rac biscyclopentadienyl Group 4 metaldiene complex.

In a further embodiment, the corresponding halide containing complex canbe regenerated in the highly pure ansa-rac biscyclopentadienyl form bycontacting the ansa-rac biscyclopentadienyl diene complex with anhalogenating agent, such as hydrochloric acid or BCl₃. Such a process ishighly desirable in order to form catalyst components thatpreferentially form isotactic polymers of prochiral olefins, such aspropylene.

Stated in more detail, the foregoing process comprises combining in asolvent in any order:

1) a mixture of rac- and meso-diastereomers of a compound having theformula: ##STR4##

wherein:

M is titanium, zirconium or hafnium;

X is halo, C₁₋₆ hydrocarbyl, C₁₋₆ hydrocarbyloxy, or di C₁₋₆hydrocarbylamido;

E, R'" and x are as previously defined, and R' and R" in each occurrenceare independently selected from the group consisting of hydrogen,hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, saidR' and R" having up to 20 non-hydrogen atoms each, or adjacent R' groupsand/or adjacent R" groups (when R' and R" are not hydrogen, halo orcyano) together form a divalent derivative (i.e., a hydrocarbadiyl,siladiyl or germadiyl group) or one R' and one R" together (when R' andR" groups are not hydrogen halo or cyano) combine to form a divalentradical (i.e., a hydrocarbadiyl, germadiyl or siladiyl group) linkingthe two cyclopentadienyl groups,

2) a C₄₋₄₀ conjugated diene, D, and

3) optionally when X is C₁₋₆ hydrocarbyl, otherwise not optionally, areducing agent;

and recovering the resulting rac-diastereomer of the formula: ##STR5##

Preferred starting complexes are diastereomeric mixtures of bis(indenyl)metallocenes, corresponding to the formula: ##STR6## or hydrogenatedderivatives thereof, wherein,

M, X, E, x, and R'" are as previously defined, and

R in each occurrence is independently selected from the group consistingof hydrogen, hydrocarbyl, silyl, germyl and combinations thereof, said Rhaving up to 20 non-hydrogen atoms each, or adjacent R groups on eachseparate indenyl system together form a divalent derivative (i.e., ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a furtherfused ring. Examples of suitable precursor compounds are found in W.Spaleck, et al., Organomet., 13, 954-963 (1994).

The complexes are rendered catalytically active by combination with oneor more activating cocatalysts, by use of an activating technique, or acombination thereof. Suitable activating cocatalysts for use hereininclude polymeric or oligomeric alumoxanes, especially methylalumoxane,triisobutyl aluminum modified methylalumoxane, or diisobutylalumoxane;strong Lewis acids (the term "strong Lewis acid" as used herein isdefined as trihydrocarbyl substituted Group 13 compounds, especiallytri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds andhalogenated derivatives thereof, having from 1 to 10 carbons in eachhydrocarbyl or halogenated hydrocarbyl group, more especiallyperfluorinated tri(aryl)boron compounds, and most especiallytris(pentafluorophenyl)borane); amine, phosphine, aliphatic alcohol andmercaptan adducts of halogenated tri(C₁₋₁₀ hydrocarbyl)boron compounds,especially such adducts of perfluorinated tri(aryl)boron compounds;nonpolymeric, ionic, compatible, noncoordinating, activating compounds(including the use of such compounds under oxidizing conditions); bulkelectrolysis (explained in more detail hereinafter); and combinations ofthe foregoing activating cocatalysts and techniques. The foregoingactivating cocatalysts and activating techniques have been previouslytaught with respect to different metal complexes in the followingreferences: EP-A-277,003, U.S. Pat. No. 5,153,157, U.S. Pat. No.5,064,802, EP-A-468,651 (equivalent to U.S. Ser. No. 07/547,718),EP-A-520,732 (equivalent to U.S. Ser. No. 07/876,268), and WO 93/23412(equivalent to U.S. Ser. No. 07/884,966 filed May 1, 1992) the teachingsof which are hereby incorporated by reference.

Combinations of strong Lewis acids, especially the combination of atrialkyl aluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to10 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane; further combinations of such strong Lewisacid mixtures with a polymeric or oligomeric alumoxane; and combinationsof a single strong Lewis acid, especially tris(pentafluorophenyl)boranewith a polymeric or oligomeric alumoxane are especially desirableactivating cocatalysts.

When utilizing such strong Lewis acid cocatalysts to polymerize higherα-olefins, especially propylene, to form homopolymers thereof, it hasbeen found especially desirable to also contact the catalyst/cocatalystmixture with a small quantity of ethylene or hydrogen (preferably atleast one mole of ethylene or hydrogen per mole of metal complex,suitably from 1 to 100,000 moles of ethylene or hydrogen per mole ofmetal complex). This contacting may occur before, after orsimultaneously to contacting with the higher α-olefin. If the foregoingLewis acid activated catalyst compositions are not treated in theforegoing manner, either extremely long induction periods areencountered or no polymerization at all results. The ethylene orhydrogen may be used in a suitably small quantity such that nosignificant affect on polymer properties is observed. For example,polypropylene having physical properties equal to or superior topolypropylene prepared by use of other metallocene catalyst systems isprepared according to the present invention.

Thus the invention further comprises an activated polymerizationcatalyst system comprising in combination:

a) a metal complex corresponding to the formula:

    CpCp'MD

wherein:

M, Cp, Cp', and D are as previously defined,

b) a Lewis acid, and

c) ethylene or hydrogen,

the quantity of ethylene or hydrogen being at least equal to thequantity necessary to activate the catalyst system for polymerization ofa C₃ or higher α-olefin, preferably at least 1 mole per mole of metalcomplex, more preferably from 1 to 100,000 moles per mole of metalcomplex.

The technique of bulk electrolysis involves the electrochemicaloxidation of the metal complex under electrolysis conditions in thepresence of a supporting electrolyte comprising a noncoordinating, inertanion. In the technique, solvents, supporting electrolytes andelectrolytic potentials for the electrolysis, are used such thatelectrolysis byproducts that would render the metal complexcatalytically inactive are not substantially formed during the reaction.More particularly, suitable solvents are materials that are liquidsunder the conditions of the electrolysis (generally temperatures from 0to 100° C.), capable of dissolving the supporting electrolyte, andinert. "Inert solvents" are those that are not reduced or oxidized underthe reaction conditions employed for the electrolysis. It is generallypossible in view of the desired electrolysis reaction to choose asolvent and a supporting electrolyte that are unaffected by theelectrical potential used for the desired electrolysis. Preferredsolvents include difluorobenzene (ortho, meta, or para isomers),dimethoxyethane, and mixtures thereof.

The electrolysis may be conducted in a standard electrolytic cellcontaining an anode and cathode (also referred to as the workingelectrode and counter electrode respectively). Suitable materials ofconstruction for the cell are glass, plastic, ceramic and glass coatedmetal. The electrodes are prepared from inert conductive materials, bywhich are meant conductive materials that are unaffected by the reactionmixture or reaction conditions. Platinum or palladium are preferredinert conductive materials. Normally an ion permeable membrane such as afine glass frit separates the cell into separate compartments, theworking electrode compartment and counter electrode compartment. Theworking electrode is immersed in a reaction medium comprising the metalcomplex to be activated, solvent, supporting electrolyte, and any othermaterials desired for moderating the electrolysis or stabilizing theresulting complex. The counter electrode is immersed in a mixture of thesolvent and supporting electrolyte. The desired voltage may bedetermined by theoretical calculations or experimentally by sweeping thecell using a reference electrode such as a silver electrode immersed inthe cell electrolyte. The background cell current, the current draw inthe absence of the desired electrolysis, is also determined. Theelectrolysis is completed when the current drops from the desired levelto the background level. In this manner, complete conversion of theinitial metal complex can be easily detected.

Suitable supporting electrolytes are salts comprising a cation and aninert, compatible, noncoordinating anion, A⁻. Preferred supportingelectrolytes are salts corresponding to the formula

    G.sup.+ A.sup.-

wherein:

G⁺ is a cation which is nonreactive towards the starting and resultingcomplex; and

A⁻ is a noncoordinating, compatible anion.

Examples of cations, G⁺, include tetrahydrocarbyl substituted ammoniumor phosphonium cations having up to 40 nonhydrogen atoms. A preferredcation is the tetra-n-butylammonium cation.

During activation of the complexes of the present invention by bulkelectrolysis the cation of the supporting electrolyte passes to thecounter electrode and A⁻ migrates to the working electrode to become theanion of the resulting oxidized product. Either the solvent or thecation of the supporting electrolyte is reduced at the counter electrodein equal molar quantity with the amount of oxidized metal complex formedat the working electrode. Preferred supporting electrolytes aretetrahydrocarbylammonium salts of tetrakis-(perfluoro-aryl) borateshaving from 1 to 10 carbons in each hydrocarbyl group, especiallytetra-n-butylammonium tetrakis(pentafluorophenyl) borate.

Suitable compounds useful as a cocatalyst in one embodiment of thepresent invention comprise a cation which is a Bronsted acid capable ofdonating a proton, and an inert, compatible, noncoordinating, anion, A⁻.Preferred anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which is formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are, of course, well knownand many, particularly such compounds containing a single boron atom inthe anion portion, are available commercially. Therefore, said singleboron atom compounds are preferred.

Preferably such cocatalysts may be represented by the following generalformula:

    (L*-H).sup.+.sub.d (A.sup.d-)

wherein:

L* is a neutral Lewis base;

(L*-H)⁺ is a Bronsted acid;

A^(d-) is a noncoordinating, compatible anion having a charge of d-, and

d is an integer from 1 to 3.

More preferably A^(d-) corresponds to the formula:

    (M'.sup.k+ Q.sub.n).sup.d-

wherein:

k is an integer from 1 to 3;

n is an integer from 2 to 6;

n-k=d;

M' is an element selected from Group 13 of the Periodic Table of theElements; and

Q independently each occurrence is selected from hydride, dialkylamido,halide, alkoxide, aryloxide, hydrocarbyl, andhalosubstituted-hydrocarbyl radicals, said Q having up to 20 carbonswith the proviso that in not more than one occurrence is Q halide.

In a more preferred embodiment, d is one, i.e. the counter ion has asingle negative charge and corresponds to the formula A⁻. Activatingcocatalysts comprising boron which are particularly useful in thepreparation of catalysts of this invention may be represented by thefollowing general formula:

    (L*-H).sup.+ (BQ'.sub.4).sup.-

wherein:

L* is as previously defined;

B is boron in an oxidation state of 3; and

Q' is a fluorinated C₁₋₂₀ hydrocarbyl group.

Most preferably, Q' is in each occurrence a fluorinated aryl group,especially a pentafluorophenyl group.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this invention are tri-substituted ammonium salts such as:

trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate,tripropylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(t-butyl)ammonium tetraphenylborate,N,N-dimethylanilinium tetraphenylborate, N,N-diethylaniliniumtetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl) borate,triethylammonium tetrakis(pentafluorophenyl) borate, tripropylammoniumtetrakis(pentafluorophenyl) borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl) borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl) borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl) borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl) borate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate,triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate,tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate,tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate,dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate,N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl) borate,N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, andN,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl) borate;

dialkyl ammonium salts such as: di-(i-propyl)ammoniumtetrakis(pentafluorophenyl) borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl) borate; and

tri-substituted phosphonium salts such as: triphenylphosphoniumtetrakis(pentafluorophenyl) borate, tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl) borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate.

Preferred [L*-H]⁺ cations are N,N-dimethylanilinium andtributylammonium.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:

    (Ox.sup.e+).sub.d (A.sup.d-).sub.e

wherein:

Ox^(e+) is a cationic oxidizing agent having a charge of e⁺ ;

e is an integer from 1 to 3; and

A^(d-), and d are as previously defined.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred embodimentsof A^(d-) are those anions previously defined with respect to theBronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a compoundwhich is a salt of a carbenium ion and a noncoordinating, compatibleanion represented by the formula:

    ©.sup.+ A.sup.-

wherein:

©⁺ is a C₁₋₂₀ carbenium ion; and

A⁻ is as previously defined. A preferred carbenium ion is the tritylcation, i.e. triphenylcarbenium.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:

    R#.sub.3 Si(X#).sub.s.sup.+ A.sup.-

wherein:

R# is C₁₋₂₀ hydrocarbyl,

s is 0 or 1,

X# is a neutral Lewis base, and

A⁻ is as previously defined.

Preferred silylium salt activating cocatalysts are trimethylsilyliumtetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate and ether substituted adducts thereof.Silylium salts have been previously generically disclosed in J. ChemSoc. Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al.,Organometallics, 1994, 13, 2430-2443. The use of the above silyliumsalts as activating cocatalysts for addition polymerization catalysts isclaimed in U.S. patent application Ser. No. 08/304,314, filed Sep. 12,1994.

The foregoing activating technique and ion forming cocatalysts are alsopreferably used in combination with a tri(hydrocarbyl)aluminum compoundhaving from 1 to 4 carbons in each hydrocarbyl group, an oligomeric orpolymeric alumoxane compound, or a mixture of a tri(hydrocarbyl)aluminumcompound having from 1 to 4 carbons in each hydrocarbyl group and apolymeric or oligomeric alumoxane.

The molar ratio of catalyst/cocatalyst employed preferably ranges from1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferablyfrom 1:1000 to 1:1. In a particularly preferred embodiment of theinvention the cocatalyst can be used in combination with a C₃₋₃₀trihydrocarbyl aluminum compound or oligomeric or polymeric alumoxane.Mixtures of activating cocatalysts may also be employed. It is possibleto employ these aluminum compounds for their beneficial ability toscavenge impurities such as oxygen, water, and aldehydes from thepolymerization mixture. Preferred aluminum compounds include C₂₋₆trialkyl aluminum compounds, especially those wherein the alkyl groupsare ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl, orisopentyl, and methylalumoxane, modified methylalumoxane anddiisobutylalumoxane. The molar ratio of aluminum compound to metalcomplex is preferably from 1:10,000 to 1000:1, more preferably from1:5000 to 100:1, most preferably from 1:100 to 100:1.

The combination of the CpCp'MD complexes with strong Lewis acidactivating cocatalysts in a preferred embodiment corresponds to one ofthe two zwitterionic equilibrium structures of the formula: ##STR7##wherein:

M is titanium, zirconium or hafnium in the +4 formal oxidation state;

Cp and Cp' are each substituted or unsubstituted cyclopentadienyl groupbound in an η⁵ bonding mode to M, said substituted cyclopentadienylgroup being substituted with from one to five substituents independentlyselected from the group consisting of hydrocarbyl, silyl, germyl, halo,cyano, and mixtures thereof, said substituent having up to 20nonhydrogen atoms, or optionally, two such substituents other than cyanoor halo together cause Cp or Cp' to have a fused ring structure, or onesubstituent on Cp and Cp' forms a linking moiety joining Cp and Cp';

Q independently each occurrence is selected from hydride, dialkylamido,halide, alkoxide, aryloxide, hydrocarbyl, andhalosubstituted-hydrocarbyl radicals, said Q having up to 20 carbonswith the proviso that in not more than one occurrence is Q halide;

R₁, R₂, R₃, R₄, R₅ and R₆ are independently hydrogen, hydrocarbyl, silyland combinations thereof, each of said R₁ to R₆ having up to 20nonhydrogen atoms; and

B is boron in a valence state of 3.

Preferred zwitterionic equilibrium structures correspond to the formula:##STR8## wherein:

R₁, R₂, R₅ and R₆ are hydrogen;

R₃ and R₄ are hydrogen, C₁₋₄ alkyl or phenyl,

M is zirconium in the +4 formal oxidation state, and

R' and R" in each occurrence are independently selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R' and R" having up to 20 non-hydrogen atomseach, or adjacent R' groups and/or adjacent R" groups (when R' and R"are not hydrogen, halo or cyano) together form a divalent derivative(i.e., a hydrocarbadiyl, siladiyl or germadiyl group which forms a fusedring system) or one R' and one R" together (when R' and R" groups arenot hydrogen halo or cyano) combine to form a divalent radical (i.e., ahydrocarbadiyl, germadiyl or siladiyl group) linking the twocyclopentadienyl groups.

Most highly preferred are the equilibrium zwitterionic metalcoordination complexes corresponding to the formula: ##STR9## wherein:

M is zirconium in the +4 formal oxidation state;

R₁, R₂, R₅ and R₆ are hydrogen;

R₃ and R₄ are hydrogen or methyl; and

R' and R" in each occurrence are independently selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R' and R" having up to 20 non-hydrogen atomseach, or adjacent R' groups and/or adjacent R" groups (when R' and R"are not hydrogen, halo or cyano) together form a divalent derivative(i.e., a hydrocarbadiyl, siladiyl or germadiyl group which forms a fusedring system) or one R' and one R" together (when R' and R" groups arenot hydrogen halo or cyano) combine to form a divalent radical (i.e., ahydrocarbadiyl, germadiyl or siladiyl group) linking the twocyclopentadienyl groups.

The catalysts may be used to polymerize ethylenically and/oracetylenically unsaturated monomers having from 2 to 20 carbon atomseither alone or in combination. Preferred monomers include the C₂₋₁₀α-olefins especially ethylene, propylene, isobutylene, 1-butene,1-hexene, 4-methyl-1-pentene, and 1-octene and mixtures thereof. Otherpreferred monomers include vinylcyclohexene, vinylcyclohexane, styrene,C₁₋₄ alkyl substituted styrene, tetrafluoroethylene,vinylbenzocyclobutane, ethylidenenorbornene, piperylene and1,4-hexadiene.

When the present bridged cyclopentadienyl polymerization catalysts areused to polymerize prochiral olefins, syndiotactic or isotactic polymersare attainable. As used herein, the term "syndiotactic" refers topolymers having a stereoregular structure of greater than 50 percent,preferably greater than 75 percent syndiotactic of a racemic triad asdetermined by ¹³ C nuclear magnetic resonance spectroscopy. Conversely,the term "isotactic" refers to polymers having a stereoregular structureof greater than 50 percent, preferably greater than 75 percent isotacticof a meso triad as determined by ¹³ C nuclear magnetic resonancespectroscopy. Such polymers may be usefully employed in the preparationof articles and objects having an extremely high resistance todeformation due to the effects of temperature via compression molding,injection molding or other suitable technique.

The ethylene/1-olefin copolymers of the present invention arecharacteristic of the type of ethylene polymers that can be obtainedwith metallocene catalysts. The polyolefins that can be produced withthe catalysts of the present invention range from elastomeric toplastomeric, i.e., substantially non-elastomeric products, depending onthe monomers, monomer amounts and polymerization conditions employed. Asused herein the term "elastomeric" is meant to signify polymers havingtensile modulus values as measured by ASTM D-638 of less than 15,000N/cm², preferably less than 5000 N/cm², and most preferably less than500 N/cm². These products find application in all the uses heretoforedeveloped for such polyolefins and can be fabricated into such end-useproducts by the methods heretofore developed for polyolefins including,for example, molding, casting, extrusion and spinning. The polyolefinsobtained with the catalysts of the present invention are useful in suchend-use applications as films for packaging, including shrink wrapapplications, foams, coating, insulating devices, including for wire andcable, and household items. The polyolefins made with the catalysts ofthe present invention can be shown to have superior properties in theseapplications over heretofore used materials in these applications usingthe tests that have been established to measure performance in theintended end-use or by tests not heretofore applied to measureperformance in such end-use applications.

In general, the polymerization may be accomplished at conditions wellknown in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions, i.e., temperatures from 0-250° C. andpressures from atmospheric to 3000 atmospheres. Suspension, solution,slurry, gas phase or high pressure, whether employed in batch orcontinuous form or under other process conditions, including therecycling of condensed monomers or solvent, may be employed if desired.Examples of such processes are well known in the art for example, WO88/02009-A1 or U.S. Pat. No. 5,084,534, disclose conditions that can beemployed with the polymerization catalysts of the present invention. Asupport, especially silica, alumina, or a polymer (especiallypolytetrafluoroethylene or a polyolefin) may be employed, and desirablyis employed when the catalysts are used in a gas phase polymerizationprocess. Such supported catalysts are generally not affected by thepresence of liquid aliphatic or aromatic hydrocarbons such as may bepresent under the use of condensation techniques in a gas phasepolymerization process. Methods for the preparation of supportedcatalysts are disclosed in numerous references, examples of which areU.S. Pat. Nos. 4,808,561, 4,912,075, 5,008,228, 4,914,253, and 5,086,025and are suitable for the preparation of supported catalysts of thepresent invention.

In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10⁻¹² :1 to 10⁻¹ :1,more preferably from 10⁻¹² :1 to 10⁻⁵ :1.

Suitable solvents for solution, suspension, slurry or high pressurepolymerization processes are noncoordinating, inert liquids. Examplesinclude straight and branched-chain hydrocarbons such as isobutane,butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclicand alicyclic hydrocarbons such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof;perfluorinated hydrocarbons such as perfluorinated C₄₋₁₀ alkanes, andthe like and aromatic and alkyl-substituted aromatic compounds such asbenzene, toluene, xylene and the like. Suitable solvents also includeliquid olefins which may act as monomers or comonomers includingethylene, propylene, butadiene, cyclopentene, 1-hexene,3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene,1-decene, styrene, divinylbenzene, allylbenzene, vinyltoluene (includingall isomers alone or in admixture), and the like. Mixtures of theforegoing are also suitable.

The catalysts may also be utilized in combination with at least oneadditional homogeneous or heterogeneous polymerization catalyst inseparate reactors connected in series or in parallel to prepare polymerblends having desirable properties. An example of such a process isdisclosed in WO 94/00500, equivalent to U.S. Ser. No. 07/904,770. A morespecific process is disclosed in copending application U.S. Ser. No.08/10958, filed Jan. 29, 1993. The teachings of the foregoingpublications and pending applications are hereby incorporated byreference.

Having described the invention the following examples are provided asfurther illustration thereof and are not to be construed as limiting.Unless stated to the contrary all parts and percentages are expressed ona weight basis.

EXAMPLE 1

Preparation of bis(η⁵ -cyclopentadienyl)zirconium s-trans(η⁴ -1,4-trans,trans-diphenyl-1,3-butadiene)

In an inert atmosphere glove box, 586 mg (2.01 mmol) of (C₅ H₅)₂ ZrCl₂and 413 mg (2.00 mmol) of trans, trans-1,4-diphenyl-1,3-butadiene arecombined in 90 ml of mixed alkanes (Isopar E™, available from ExxonChemicals Inc.). To the stirred slurry is added 1.60 ml of 2.5M n-butyllithium. The mixture turns dark red immediately. After stirring at 25°C. for 2 hours, the mixture is heated to reflux for 3 hours. The warmsolution is filtered. The red solid residue is extracted with a totalvolume of 90 ml of warm toluene. The extracts are filtered and combinedwith the hexanes filtrate. The total volume of the solution isconcentrated to 40 ml under reduced pressure. At this point a redprecipitate is formed. The mixture is warmed until the solid redissolvesand the solution is placed in a freezer (-25° C.). Dark red crystals aresubsequently collected on a glass frit. Drying under reduced pressuregives 210 mg (25 percent yield) of (C₅ H₅)₂ Zr(η⁴ -1,4-trans,trans-diphenyl-1,3-butadiene) as verified by ¹ H NMR analysis. Theproduct has a 95 percent s-trans, 5 percent s-cis-configuration.

EXAMPLE 2

Preparation of bis(η⁵ -cyclopentadienyl)zirconiums-cis(2,3-dimethyl-1,3-butadiene)

In an inert atmosphere glove box, 586 mg (2.01 mmol) of (C₅ H₅)₂ ZrCl₂and 2.5 ml (22 mmol) of 2,3-dimethyl-1,3-butadiene are combined in 90 mlof mixed alkanes. To the stirred slurry is added 1.60 ml of 2.5M n-butyllithium. The color changes to red slowly. After stirring for 1 hr at 25°C., the mixture is heated to reflux for 1/2 hr. The warm solution isthen filtered using Celite™ brand diatomaceous earth filter aidavailable from Fisher Scientific Inc. The filtrate is concentrated to 50ml and the deep red filtrate placed in the freezer (-25° C.). Darkcrystals are collected by filtration and dried under reduced pressure togive 234 mg (39 percent yield) of (C₅ H₅)₂Zr(2,3-dimethyl-1,3-butadiene) as verified by ¹ H NMR analysis. Theproduct has a s-cis-configuration for the diene.

EXAMPLE 3

Combination of Lewis Acid with bis(cyclopentadienyl)zirconium s-trans(η⁴-1,4-trans, trans-diphenyl-1,3-butadiene)

In an inert atmosphere glove box, 8.4 mg (0.020 mmol) of (C₅ H₅)₂ Zrs-trans(η⁴ -1,4-trans, trans-diphenyl-1,3-butadiene) of Preparation #1and 10.0 mg (0.020 mmol) of B(C₆ F₅)₃ is combined in 0.75 ml ofbenzene-d₆ to form a homogeneous solution. Analysis by ¹ H NMR shows thereactants to be completely consumed.

EXAMPLE 4

Combination of Lewis Acid with bis(cyclopentadienyl)zirconiums-cis(2,3-dimethyl-1,3-butadiene)

In an inert atmosphere glove box, 5.9 mg (0.0195 mmol) of (C₅ H₅)₂Zr(2,3-dimethyl-1,3-butadiene) and 10.0 mg (0.0195 mmol) of B(C₆ F₅)₃ iscombined in 0.75 ml of benzene-d₆ to give a homogeneous solution. ¹ HNMR analysis indicated that the mixture had been cleanly converted tothe zwitterionic compound, (C₅ H₅)₂ Zr+(CH₂ CMe═CMeCH₂ B(C₆ F₅)₃ ⁻) orits η³ equivalent isomer. δ (C₆ D₆), 5.31 (s, 5H), 4.91 (s, 5H), 2.37(d, 10.5 Hz, 1H), 1.09 (s, 3H), 0.93 (d, 10.5 Hz), -0.3 (broad) and -0.7ppm (broad).

EXAMPLE 5

Polymerization using a Combination of (C₅ H₅)₂ Zr s-trans(η⁴ -1,4-trans,trans-diphenyl-1,3-butadiene) and B(C₆ F₆)₃

A two-liter reactor is charged with 746 g of mixed alkanes and 120 g of1-octene comonomer. Hydrogen is added as a molecular weight controlagent by differential pressure expansion from a 75 ml addition tank from300 psig (2.1) MPa) to 275 psig (1.9 MPa). The reactor is heated to thepolymerization temperature of 140° C. and saturated with ethylene at 500psig (3.4 MPs). 5.00 μmol of the catalyst combination of Example 3(0.00500M solutions in toluene) is transferred to a catalyst additiontank. The polymerization is initiated by injecting this solution intothe contents of the reactor. The polymerization conditions aremaintained for 10 minutes with ethylene provided on demand at 500 psi(3.4 MPa). The polymer solution is removed from the reactor and combinedwith 100 mg of a hindered phenol anti-oxidant (Irganox™ 1010 availablefrom Ciba Geigy Corp.). Volatiles are removed from the polymer in avacuum oven set at 120° C. for about 20 hours. The polymer yield is 16.8g.

EXAMPLE 6

Preparation of Ethylene/Propylene Copolymer using[bis(cyclopentadienyl)]zirconium (2,3-dimethyl-1,3-butadiene) and B(C₆F₅)₃

A two liter reactor is charged with 656 g of mixed alkanes and 207 g ofpropylene comonomer. Hydrogen was added by differential pressureexpansion from a 75 ml additional tank from 300 psig (2.1 MPa) to 274psig (1.9 MPa). The reactor is heated to the polymerization temperatureof 140° C. and saturated with ethylene at 500 psig (3.4 MPa). 10 μmol of[bis(cyclopentadienyl)]zirconium (2,3-dimethyl-1,3-butadiene) and 10μmol B(C₆ F₅)₃ in toluene is transferred to a catalyst addition tank.The polymerization is initiated by injecting this solution into thecontents of the reactor. The polymerization conditions are maintainedfor 20 minutes with ethylene provided on demand at 500 psi (3.4 MPa).The reaction mixture was removed from the reactor and the volatiles wereremoved in a vacuum oven set at 120° C. for about 20 hours 21.0 g Of anethylene/propylene copolymer was obtained.

EXAMPLE 7

Combination of (C₅ H₅)₂ Zr s-trans(η⁴ -1,4-trans,trans-diphenyl-1,3-butadiene) with DimethylaniliniumTetrakis(pentafluorophenyl) Borate

In an inert atmosphere glove box, 0.043 g (0.010 mmol) ofbis-cyclopentadienyl zirconium s-trans(η⁴ -1,4-trans,trans-diphenyl-1,3-butadiene) is dissolved in 20 ml of toluene followedby addition of 0.0780 g (0.099 mmol) of dimethylaniliniumtetrakis(pentafluorophenyl) borate using 10 ml of toluene to wash thesolids into the reaction flask. After one hour the solvent is removedunder reduced pressure. The product is washed with pentane (3×10 ml withdrying after the final wash). The product is isolated as an oil.

EXAMPLE 8

Electrolytic Preparation of [(C₅ H₅)₂ Zr s-trans(η⁴ -1,4-trans,trans-diphenyl-1,3-butadiene)] [tetrakis(pentafluorophenyl) borate]

A standard H-cell for electrolysis comprising two electrode wellsseparated by a fine glass frit, platinum mesh working and counterelectrodes, and a silver reference electrode is placed inside an inertatmosphere glove box filled with argon. Each half of the cell is filledwith 1,2-difluorobenzene solvent (5 ml in the working compartment, 4 mlin the counter compartment) and tetra-n-butylammoniumtetrakis(pentafluorophenyl) borate supporting electrolyte (8 mmol). Thecomplex, bis(cyclopentadienyl)Zr s-trans(η⁴ -1,4-trans,trans-diphenyl-1,3-butadiene) (0.017 g) is placed in the workingcompartment. A sweep of the working electrode potential is used todetermine the voltage to be applied during electrolysis. The solution isstirred and the potential is stepped to the first oxidation wave of thecomplex and adjusted to obtain a 1.5 mA current. The applied potentialis turned off when the current drops to 30 percent of its original valuehaving passed a total of 3.3 coulombs. This represents a conversion of72 percent. The working compartment solution is then pipetted into around bottom flask and the solvent is removed under vacuum. Theresulting solid product is extracted with toluene (2.0 ml) and isdirectly transferred to the polymerization reaction in Example 9.

EXAMPLE 9

Polymerization using Catalyst of Example 8

A 2 L stirred reactor is charged with the desired amounts of mixedalkanes solvent and 15 g 1-octene comonomer. Hydrogen is added as amolecular weight control agent by differential pressure expansion (25Δpsi (200 ΔkPa)) from an approximately 75 ml addition tank at 300 psi(2.1 MPa). The reactor is heated to the polymerization temperature andsaturated with ethylene at 500 psi (3.4) MPa. 5.00 μmol of the catalystof Example 8 dissolved in toluene is transferred to a catalyst additiontank and injected into the reactor. The polymerization is allowed toproceed for the desired time with ethylene provided on demand at 500 psi(3.4 MPa). After 15 minutes run time, the solution is removed from thereactor and quenched with isopropanol. A hindered phenol anti-oxidant isadded to the polymer solution. The resulting solid polymer of ethyleneand 1-octene is dried in a vacuum oven set at 120° C. for about 20hours.

EXAMPLE 10

Polymerization using (C₅ H₅)₂ Zr s-trans(η⁴ -1,4-trans,trans-diphenyl-1,3-butadiene) with Alumoxane

A stirred 5 L autoclave reactor is charged with 1850 g of anhydroushexane through a mass-flow meter. A solution containing 100 μmols oftriisopropylaluminum modified methylalumoxane (MMAO, obtained from AkzoCorporation) in 10 ml of hexane is then added to the reactor via apressurized stainless steel cylinder prior to heating to 80° C. At thispoint the reactor pressure is increased to 10 psig (70 kPa) by theaddition of hydrogen followed by ethylene sufficient to bring the totalpressure to 175 psig (1.21 Mpa). The ethylene is supplied continuouslyto the reactor by a demand feed regulator on the line. 12.5 μmol of thediene complex of Example 1 is slurried in hexane and is then added tothe reactor to initiate the polymerization. After 30 minutes theethylene flow is stopped and the reactor is vented and cooled. Theresulting polyethylene is filtered and dried at 80° C. overnight in avacuum oven.

EXAMPLE 11

Preparation of rac-[1,2-ethanediylbis(1-indenyl)]zirconium s-trans-(η⁴-1,4-trans,trans-diphenyl-1,3-butadiene)

In an inert atmosphere glove box, 837 mg (2.00 mmol) ofrac-[1,2-ethanediylbis(1-indenyl)]zirconium dichloride and 413 mg (2.00mmol) of trans,trans-1,4-diphenyl-1,3-butadiene were combined inapproximately 90 ml mixed alkanes. To this mixture was added 1.60 ml of2.5M butyl lithium in mixed alkanes (4.00 nmol). This mixture turneddark red immediately. After stirring at ambient temperature for one halfhour the mixture was heated to reflux for two and one half hours. Thesolution was cooled and filtered through Celite™ brand filtration aid.The solid residue was extracted using a total of 100 ml of toluene. Theextracts were filtered and the filtrates were combined. The filtrate wasconcentrated to 20 ml under reduced pressure and the concentrate cooledto 30° C. A red solid was collected on a glass frit. The volatiles wereremoved from the solid under reduced pressure to give 767 mg of a redcrystalline solid. The identity and purity of the compound was confirmedusing ¹ H NMR spectroscopy. δ(C₆ D₆), 7.55 (d, 8.8 Hz, 2H), 7.2 (m),7.3-6.8 (m, 4H), 6.76 (m, 2H), 6.60 (d, 8.5 Hz, 2H), 5.23 (d, 3.3 Hz,2H), 4.58 (d, 3.3 Hz, 2H), 3.35 (m, 2H), 3.01 (m, 4H) and 1.83 ppm (m,2H).

EXAMPLE 12

Combination of Lewis Acid withrac-[1,2-ethanediylbis(1-indenyl)]zirconium s-trans(η⁴-1,4-trans,trans-diphenyl-1,3-butadiene)

In an inert atmosphere glove box, 9 mg (˜0.2 mmol) ofrac-[bis-1,2-ethanediylbis(1-indenyl)]zirconium s-trans(η⁴ -1,4-trans,trans-diphenyl-1,3-butadiene) and 10 mg (0.02 mmol) of B(C₆ F₅)₃ iscombined with 0.75 mL of benzene-d₆ to give a homogeneous solution ofthe complex as established by ¹ H NMR analysis. The dissolved reactionproduct is useful as a polymerization catalyst for the polymerization ofethylene following the procedure of Example 10.

EXAMPLE 13

Preparation ofbis(n-butylcyclopentadienyl)zirconium-s-cis(2,3-dimethyl-1,3-butadiene)

In an inert atmosphere glove box, 2.01 mmol of (n-butyl C₅ H₄)₂ ZrCl₂and 22 mmol of 2,3-dimethyl-1,3-butadiene are combined in 90 ml ofhexane. To the stirred slurry is added 1.60 ml of 2.5M n-butyl lithium.The color changes to red slowly. After stirring for 1 hr at roomtemperature, the mixture is heated to reflux for 1/2 hr. The warmsolution is then filtered using a diatomaceous earth filter aid. Thefiltrate is concentrated to 50 ml and the deep red filtrate placed inthe freezer (-25° C.). Dark crystals are collected by filtration anddried under reduced pressure to give (n-butyl C₅ H₄)Zrs-cis(2,3-dimethyl-1,3-butadiene) based on ¹ H NMR analysis.

EXAMPLE 14

Combination of Lewis Acid with bis(n-butylcyclopentadienyl)zirconiums-cis(2,3-dimethyl-1,3-butadiene)

In an inert atmosphere glove box, 0.0195 mmol of (n-butyl C₅ H₄)₂Zr(2,3-dimethyl-1,3-butadiene) and 0.0195 mmol of B(C₆ F₅)₃ is combinedin 0.75 ml of benzene-d₆ to give a homogeneous solution. The conversionto (n-butyl C₅ H₄)₂ Zr⁺ (CH₂ CMe═CMeCH₂ B(C₆ F₅)₃ ⁻ or its η³ equivalentisomer) is established by ¹ H NMR analysis. The resulting product isuseful as a catalyst for the polymerization of ethylene as described inExample 10.

EXAMPLE 15

Preparation ofrac[dimethylsilanediylbis(1-(2-methyl-4-phenyl)indenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene)

In an inert atmosphere glove box, 106.6 mg (0.170 mmol) ofrac-[dimethylsilanediylbis(1-(2-methyl-4-phenyl)indenyl)]zirconiumdichloride and 35.1 mg (0.170 mmol) oftrans,trans-1,4-diphenyl-1,3-butadiene were combined in approximately 50ml toluene. To this mixture was added 0.14 ml of 2.5M butyl lithium inmixed alkanes (0.35 mmol). After stirring at about 25° C. for two hoursthe mixture had turned from yellow to orange. The mixture was heated intoluene (about 80° C.) for three hours during which time it had turneddark red. The solution was cooled and filtered through Celite™ brandfilter aid. The volatiles were removed from the solid under reducedpressure to give a red solid. This was dissolved in 15 ml mixed alkaneswhich was then removed under reduced pressure. ¹ H NMR spectroscopyshowed the desired n-diene product as well as some butylated material.The solid residue was dissolved in toluene and heated to reflux for fivehours. Volatiles were then removed under reduced pressure and theresidue dissolved in a small amount of mixed alkanes (ca 10 ml) and theresulting solution was cooled to -30° C. A solid was isolated bydecanting the solution from the solid and removing the remainingvolatiles from the solid under reduced pressure. ¹ H NMR spectroscopyshowed the desired compound,rac-[dimethylsilanediylbis(1-(2-methyl-4-phenyl)indenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) as the major componentcontaining an indenyl type ligand.

EXAMPLE 16

Preparation of Ethylene/Propylene/Diene Terpolymers

A 2 L batch reactor is charged with 500 mL of mixed alkanes, 75 mL of5-ethylidene-1-norbornene, and 500 mL of liquefied propylene. Thereactor is heated to 60° C., and is saturated with ethylene at 500 psig(3.4 MPa). In an inert atmosphere drybox, 10 μmol of a 0.005M solutionin toluene ofrac-[dimethylsilanediylbis(1-(2-methyl-4-phenyl)indenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and 10 μmol of a 0.005 msolution of B(C₆ F₅)₃ in toluene are combined and the mixture istransferred to the reactor to initiate polymerization. After 15 minutes,the reactor is vented and the solution is drained from the reactor. Thepolymer solution is combined with 100 mg of antioxidant and thevolatiles are removed under reduced pressure in order to isolate therubbery terpolymer of ethylene/propylene/ethylidene norbornene.

EXAMPLE 17

Preparation of Ethylene/Propylene/7-methyl-1,6-Octadiene Copolymer

The procedure in Example 16 is substantially followed except that 75 mLof 7-methyl-1,6-octadiene is used in place of the ethylidene norbornene.After removal of the solvent, a rubbery terpolymer ofethylene/propylene/7-methyl-1,6-octadiene is obtained.

EXAMPLE 18

Preparation of Ethylene/Propylene/Piperylene Copolymer

The procedure in Example 16 is substantially followed except that 75 mLof piperylene (1,3-pentadiene) is used in place of the ethylidenenorbornene. After removal of the solvent, a rubbery terpolymer ofethylene/propylene/piperylene is obtained.

EXAMPLE 19

Preparation of Isotactic Polypropylene

A two liter reactor is charged with 500 mL of mixed alkanes, and 500 mLof liquefied propylene. Ethylene (10 μmol) is added to the reactor. Thereactor is heated to 60° C., and 10 μmol of the combination ofrac-1,2-[bis-(1-indenyl)ethanediyl]zirconium s-trans(η⁴-1,4-trans-trans-diphenyl-1,3-butadiene) with B(C₆ F₅)₃ of Example 12(0.005M solution in toluene) is added slowly in order to control theexothermic polymerization. After 15 minutes polymerization at 60° C.,the reactor is vented and the reactor contents are removed. The solventis removed under vacuum and crystalline, solid isotactic polypropyleneis isolated.

EXAMPLE 20

Preparation of2,2-propanediyl(cyclopentadienyl-9-fluorenyl)zirconium(2,3-dimethyl-1,3-butadiene)

In an inert atmosphere glovebox, 5.0 g of2,2-propanediyl(cyclopentadienyl-9-fluorenyl)zirconium dichloride (11.56mmol) and 0.95 g of (2,3-dimethyl-1,3-butadiene) (11.56 mmol) (availablefrom Boulder Scientific Inc.) are combined in 500 mL of toluene. Thismixture is stirred and 9.3 mL of 2.5M n-butyl lithium is added. Afterstirring for 2 hours at room temperature, the mixture is filteredthrough a fritted funnel. Toluene is added to the fritted funnel and thesolids are extracted. The total volume of the filtrate is concentratedunder reduced pressure to obtain the product in crude form. The crudeproduct can be purified by recrystallization in order to obtain a higherpurity product.

EXAMPLE 21

Preparation of Syndiotactic Polypropylene

A two liter reactor is charged with 500 mL of mixed alkanes, and 500 mLof liquefied propylene. A small quantity of ethylene (0.001 weightpercent based on propylene) is added to the reactor. The reactor isheated to 60° C. In an inert atmosphere drybox, 10 μmol of the2,2-propanediyl(cyclopentadienyl-9-fluorenyl)zirconium(2,3-dimethyl-1,3-butadiene)(0.005M solution in toluene) is combined with 10 μmoles of B(C₆ F₅)₃(0.005M solution in toluene). This mixture is added slowly to thereactor in order to control the exothermic polymerization. After 15minutes polymerization at 60° C., the reactor is vented and the reactorcontents are removed. The solvent is removed under vacuum andcrystalline, solid syndiotactic polypropylene is isolated.

EXAMPLE 22

Preparation of Syndiotactic Polypropylene

The procedure of Example 21 is substantially followed, except that noethylene is added to the reactor and the catalyst mixture is 10 μmol of2,2-propanediyl(cyclopentadienyl-9-fluorenyl)zirconium(2,3-dimethyl-1,3-butadiene)(0.005M solution in toluene) combined with 10 mmoles ofmethylaluminoxane (MAO) (1.0M solution in toluene). This mixture isadded slowly to the reactor in order to control the exothermicpolymerization. After 15 minutes polymerization at 60° C., the reactoris vented and the reactor contents are removed. The solvent is removedunder reduced pressure and crystalline, solid syndiotactic polypropyleneis isolated.

EXAMPLE 23

Preparation of Supported Catalysts

(a) Preparation of support

Dried silica (2.5 g, Davison 948, dried at 800° C.) is slurried with 10mL of 1.0M methylaluminoxane (MAO, 1.0M in toluene) and the mixture isstirred for 30 minutes. The slurry is filtered and washed five timeswith 10 mL portions of pentane. The washed slurry is dried under vacuum.

(b) Preparation of supported catalyst

Bis(n-butylcyclopentadienyl)zirconium s-trans(η⁴-1,4-trans-trans-diphenyl-1,3-butadiene) is prepared analogously tobis(cyclopentadienyl)zirconium s-trans(η⁴-1,4-trans-trans-diphenyl-1,3-butadiene) (Example 1). A 100 mL flask ischarged with 0.50 g of bis(n-butylcyclopentadienyl)zirconium s-trans(η⁴-1,4-trans-trans-diphenyl-1,3-butadiene) (1.17 mmol). A solution of MAO(50 mL of a 1.0M solution in toluene) is added. The solution is stirredfor five minutes followed by the addition of 2.5 g of the treated silicaobtained from part (a) above. The mixture is stirred for five minutes,and the toluene is removed under vacuum to give the supported catalyst.

EXAMPLE 24

Slurry Polymerization using Supported Catalyst

A 1 L reactor is charged with 400 mL of hexane, and 0.2 mL oftriethylaluminum (1.6M in heptane). The reactor is heated to 80° C. andethylene is provided on demand at 100 psig (0.7 MPa). After the reactoris saturated with ethylene, 0.5 g of the prepared supported catalystobtained from step (b) above is added to initiate the polymerization.After 60 minutes, the reaction is stopped by venting the reactor and thesolid polyethylene is recovered.

EXAMPLE 25

Preparation ofrac-dimethylsilyl-bis(2-methyl-4-(1-napthyl)-1-indenyl)zirconiums-trans-(η⁴ -1,4-trans-trans-diphenyl-1,3-butadiene)

In an inert atmosphere glovebox, 5.0 g ofrac-dimethylsilyl-bis(2-methyl-4-(1-napthyl)-1-indenyl)-zirconiumdichloride (6.84 mmol) and 1.408 g of trans,trans-1,4-diphenyl-1,3-butadiene (6.84 mmol) are combined in 500 mL oftoluene. This mixture is stirred and 5.5 mL of 2.5M n-butyl lithium isadded. After stirring for 2 hours at room temperature, the mixture isheated to reflux for 3 hours. The warm solution is filtered through afritted funnel. Warm toluene is added to the fritted funnel and thesolids are extracted. The total volume of the filtrate is concentratedunder reduced pressure to obtain the product in crude form. The crudeproduct can be purified by recrystallization in order to obtain a higherpurity product.

EXAMPLE 26

Polymerization using Supported Catalyst

Silica (2.5 g, Davison™ 952, available from Davison Catalyst Corp.) isdried at 600° C. To this dried silica is added 25 mL of toluene in aninert atmosphere drybox. The slurry is stirred while 0.50 g ofrac-dimethylsilyl-bis(2-methyl-4-napthyl-1-indenyl)-zirconium (η⁴-1,4-trans-trans-diphenyl-1,3-butadiene) is added. After 10 minutes, thesolvent is removed under reduced pressure to give a supported catalyst.A 2 L reactor is charged with 500 mL of mixed alkanes and 500 mL ofliquefied propylene, and 5 mL of 1M methylaluminoxane (MAO) in tolueneis added. The reactor is heated to 60° C. To the reactor is added 0.50 gof the silica supported catalyst to initiate the polymerization. After30 minutes, the reactor is vented and the high melting, crystallinepolypropylene is recovered.

EXAMPLE 27

Polymerization using Unsupported Catalyst

A 2 L reactor is charged with 500 mL of mixed alkanes, 500 mL ofliquefied propylene, and 0.2 mL of triethylaluminum (1.6M in heptane) isadded. The reactor is heated to 60° C. A small quantity of ethylene(0.001 weight percent based on propylene) is added to the reactor. In aninert atmosphere drybox, 10 μmole ofbis(2-methyl-4-napthyl-1-indenyl)zirconium (η⁴-1,4-trans-trans-diphenyl-1,3-butadiene) (0.005M in toluene) is combinedwith 10 μmoles of B(C₆ F₅)₃ (0.005M solution in toluene). This mixtureis added slowly to the reactor in order to control the exothermicpolymerization. After 15 minutes polymerization at 60° C., the reactoris vented and the reactor contents are removed. The solvent is removedunder vacuum and crystalline, solid isotactic polypropylene is isolated.

EXAMPLE 28

Polymerization with N,N-dimethylaniliniumTetrakis(pentafluorophenyl)borate Activating Cocatalyst

The procedure of Example 27 is substantially repeated except that 10μmoles of a 0.005M toluene solution of N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate is used in place of the B(C₆ F₅)₃cocatalyst. After 15 minutes polymerization at 60° C., the reactor isvented and the reactor contents are removed. The solvent is removedunder vacuum and crystalline, solid isotactic polypropylene is isolated.

EXAMPLE 29

High-Pressure Polymerization

A 1000 mL stirred steel autoclave equipped to perform Zieglerpolymerizations at pressures up to 250 MPa and temperatures up to 300°C. is used. The reaction system is equipped with a thermocouple and apressure transducer to measure temperature and pressure continuously,and with means to supply purified ethylene, nitrogen, hydrogen, and1-butene. The reactor is also equipped with means for continuouslyintroducing a measured flow of catalyst solution and equipment forrapidly venting and quenching the reaction and for collecting thepolymer product. The catalyst is prepared by combining 564 mg ofbis(n-butyl-cyclopentadienyl)zirconium s-trans(η⁴-1,4-trans-trans-diphenyl-1,3-butadiene) with 1.0 L of 0.8M MAO in 10 Lof toluene in an inert atmosphere drybox. This catalyst solution iscontinuously fed into the reactor at a rate necessary to maintain atemperature of 180° C. in the reactor. During the run, ethylene and1-hexene are pressured into the reactor at a total pressure of 100 MPaat a mass flow of 50 kg/hr. The reactor is stirred at 1000 rpm. A solidcopolymer of ethylene and 1-hexene is obtained.

EXAMPLE 30

High Pressure Polymerization

The procedure of Example 29 is repeated, except that no MAO is used andthe catalyst is prepared by simultaneously adding equimolar amounts of0.005M solutions of bis(n-butylcyclopentadienyl)zirconium s-trans(η⁴-1,4-trans-trans-diphenyl-1,3-butadiene) and B(C₆ F₅)₃ to the flowingstream of 1-hexene just prior to the reactor. A solid copolymer ofethylene and 1-hexene is obtained.

EXAMPLE 31

Preparation of rac-[1,2-ethanediylbis(1-indenyl)]zirconium s-trans(η⁴-trans,trans-1,4-diphenyl-1,3-butadiene) from a Mixture of rac and meso[1,2-ethanediylbis(1-indenyl)]zirconium Dichlorides

In an inert atmosphere glove box, 418.5 mg (1.00 mmol) of[1,2-ethanediylbis(1-indenyl)]zirconium dichloride (95 percent rac, 5percent meso by ¹ H NMR analysis) and 207 mg (1.00 nmol) oftrans,trans-1,4-diphenyl-1,3-butadiene were combined in approximately.70 ml mixed alkanes. To this mixture was added 0.80 ml of 2.5M butyllithium in mixed alkanes (2.00 mmol). This mixture turned dark redimmediately. After stirring at about 25° C. for one half hour themixture was heated to reflux for three hours. The solution was cooledand filtered through Celite™ brand filter aid and the mixed alkanesfiltrate set aside. The solid residue was extracted twice with 30 mltoluene, the extracts were filtered and the filtrates combined. Thefiltrate was concentrated to 15 ml under reduced pressure and theconcentrate cooled to -30° C. A red solid was collected on a glass frit.The volatiles were removed from the solid under reduced pressure to give200 mg of a red crystalline solid. The identity and purity of thecompound was confirmed using ¹ H NMR spectroscopy and it was found notto contain any meso isomer. The toluene filtrate was combined with themixed alkanes filtrate and the volatiles were removed under reducedpressure. The solid was washed briefly with -30° C. pentane. Dryingunder reduced pressure gave a red powder. ¹ H NMR analysis showed theproduct was rac-[1,2-ethanediylbis(1-indenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) contaminated with some freediene but with no meso product.

EXAMPLE 32

Preparation of rac-[1,2-ethanediylbis(1-indenyl)]zirconium dichloridefrom rac-[1,2-ethanediylbis(1-indenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and HCl

A concentrated solution of rac-[1,2-ethanediylbis(1-indenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) was prepared in C₆ D₆ and the ¹H NMR spectrum obtained. To this deep red solution was added 0.1 ml of12M aqueous HCl. The mixture turned bright yellow quickly and yellowmicrocrystals formed on the walls of the sample tube. ¹ H NMR analysisshowed the sample was rac-[1,2-ethanediylbis(1-indenyl)]zirconiumdichloride with no meso isomer present. The solvent was decanted fromthe yellow crystals which were then washed with 0.75 ml of CDCl₃ whichwas also decanted from the remaining solid. C₆ D₆ was added to the solidand the ¹ H NMR spectrum obtained. The spectrum showed the material tobe rac-[1,2-ethanediylbis(1-indenyl)]zirconium dichloride with most ofthe organic fragments absent.

EXAMPLE 33

Preparation of rac-[1,2-ethanediylbis(1-tetrahydroindenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene)

In an inert atmosphere glove box, 213 mg (0.500 mmol) ofrac-[1,2-ethanediylbis(1-tetrahydroindenyl)]-zirconium dichloride and103 mg (0.500 mmol) of trans,trans-1,4-diphenyl-1,3-butadiene werecombined in about 35 ml mixed alkanes. To this mixture was added 0.40 mlof 2.5M butyl lithium in mixed alkanes (1.0 mmol). This mixture turneddark red gradually. After stirring at about 25° C. for one half hour themixture was heated to reflux for one half hour. The solution was cooledand filtered through Celite™ brand filter aid. The residue was washedthree times each with 10 mL of mixed alkanes. The solid residue wasextracted with toluene (five times with 12 ml each), the extracts werefiltered and the filtrates combined. Volatiles were removed from thefiltrate under reduced pressure to give 98.0 mg of a red crystallinesolid. The identity and purity of the compound was confirmed using ¹ HNMR spectroscopy. δ (C₆ D₆), 7.50 (d, 7.7 Hz, 4H), 7.29 (m, 4H), 7.02(t, 7.4 Hz, 1H), 4.70 (d, 3 Hz, 2H), 4.26 (d, 3 Hz, 2H), 3.57 (m, 2H),3.15 (m, 2H), 2.8 (m, 2H), 2.5 (m), 2.0 (m), 1.8 (m) and 1.4 ppm (m).

EXAMPLE 34

Preparation of rac-[1,2-ethanediylbis(1-indenyl)]hafnium(trans,trans-1,4-diphenyl-1,3-butadiene)

In an inert atmosphere glove box, 505.7 mg (1.00 mmol) ofrac-[1,2-ethanediylbis(1-indenyl)]hafnium dichloride and 206.3 mg (1.00mmol) of trans,trans-1,4-diphenyl-1,3-butadiene were combined in about70 ml mixed alkanes. To this mixture was added 0.80 ml of 2.5M butyllithium in mixed alkanes (2.0 mmol). This mixture turned dark orangegradually. After stirring at about 25° C. for five hours the mixture wasfiltered through Celite™ brand filter aid and the filtrate wasconcentrated under reduced pressure to an orange powder. ¹ H NMRanalysis in C₆ D₆ showed the solid to be a mixture of the dibutylhafnium complex and free diene. The solid was dissolved in 50 ml oftoluene and heated to reflux for two hours during which time thesolution became dark red. The volatiles were removed under reducedpressure. The solid residue was washed with mixed alkanes. The solid wasdried under reduced pressure to give 217 mg of a red powder. The productwas identified using ¹ H NMR spectroscopy, δ (C₆ D₆), 7.50 (d, 9.6 Hz,2H), 7.28 (m), 7.19, 6.98 (m), 6.74 (m), 6.60 (d, 8.5 Hz), 5.17 (d, 3Hz, 2H) 4.68 (d, 3 Hz, 2H), 3.36 (m, 2H), 2.96 (m) and 1.70 ppm (m, 2H).

EXAMPLE 35

Preparation of [2,2-propanediyl(1-fluorenyl)(cyclopentadienyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene)

In an inert atmosphere glove box, 433 mg (1.00 mmol) of[2,2-propanediyl(1-fluorenyl)(cyclopentadienyl)]zirconium dichloride(previously recrystallized from boiling toluene) and 206 mg (1.00 mmol)of trans,trans-1,4-diphenyl-1,3-butadiene were combined in about 60 mltoluene. To this mixture was added 0.80 ml of 2.5M butyl lithium inmixed alkanes (2.0 mmol). This mixture turned dark red immediately.After stirring at ambient temperature for one half hour the mixture wasfiltered through Celite™ brand filter aid. The filtrate was concentratedto 15 ml under reduced pressure and cooled to -30° C. A crystalline darkpurple solid was collected on a glass frit and the solid was washed oncewith cold mixed alkanes to give 226 mg of solid. The identity and purityof the compound was confirmed using ¹ H NMR spectroscopy. δ (C₆ D₆), 7.4(d), 7.25 (m), 7.0 (m), 6.85 (m), 6.6 (d), 6.55 (m), 5.6 (s), 5.1 (s)4.3 (m), 1.6 (s) and 1.2 ppm (m).

Batch Solution Polymerization Procedure Examples 36-49

All solvents and liquid monomers are sparged with nitrogen and, togetherwith any gases used, are passed through activated alumina prior to use.A two liter reactor is charged with mixed alkanes solvent and optionally1-octene or styrene comonomer. Propylene monomer, if used, is measuredusing a MicroMotion™ brand gas flow rate meter which gives total monomersupplied. Hydrogen, if desired, is added by differential pressureexpansion from a 75 ml addition tank from 300 psig (2070 Kpa) to a lowerpressure, usually 275 psig (1890 Kpa). Batch quantities of ethylene arethen added using the flow meter. If ethylene monomer is used on demand,the reactor contents are first heated to within 5° C. of thepolymerization temperature and saturated with ethylene typically at 500psig (3450 Kpa). The catalyst and cocatalyst are combined in toluene andtransferred to a catalyst addition tank. When the reactor contents areat the desired run temperature, the polymerization is initiated byinjecting the catalyst solution into the contents of the reactor. Thepolymerization temperature is maintained by external resistive heatingand internal cooling for the desired run time. The pressure ismaintained at 500 psig (3450 Kpa) if ethylene is provided on demand.Occasionally, additional catalyst and cocatalyst solution is added tothe contents of the reactor in the foregoing manner. After the desiredrun time has elapsed, the contents of the reactor are removed andcombined with hindered phenol antioxidant solution. Polymer is isolatedby removing the volatile components from the reaction mixture in avacuum oven set at from 120 to 130° C. for about 20 hours.

EXAMPLE 36

Preparation of Isotactic Polypropylene usingrac-[1,2-ethanediylbis(1-indenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and B(C₆ F₅)₃

The general procedure was followed using 719 g mixed alkanes, 26 Δpsi(170 kPa) hydrogen, 200 g propylene monomer with a temperature of 70° C.and a polymerization time of 60 minutes. The catalyst was prepared bycombining 2 μmol rac-[1,2-ethanediylbis(1-indenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and 2 μmol B(C₆ F₅)₃ intoluene. The yield of isotactic polypropylene was 181.5 g, (74 percent mpentad by ¹³ C NMR analysis).

EXAMPLE 37

Preparation of Isotactic Polypropylene usingrac-[1,2-ethanediylbis(1-indenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and B(C₆ F₅)₃ with Ethylene

The polymerization conditions of Example 36 were substantially repeatedexcepting that a small quantity of ethylene was added to the reactorcontents initially instead of hydrogen. Quantities of ingredients usedwere 723 g solvent, 3 g ethylene, 200 g propylene monomer with apolymerization temperature of 70° C. and a run time of 30 minutes. Thecatalyst was prepared by combining 2 μmolrac-[1,2-ethanediylbis(1-indenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and 2 μmol B(C₆ F₅)₃ intoluene. 94.2 g of isotactic polypropylene/ethylene copolymer wasobtained (73 percent m pentad by ¹³ C NMR analysis).

EXAMPLE 38

Preparation of Isotactic Polypropylene usingrac-[1,2-ethanediylbis(1-indenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, [Me₂ NHPh]⁺ [B(C₆ F₅)₄ ]⁻

The general procedure was followed using 715 g mixed alkanes, 25 Δpsi(170 kPa) hydrogen, 200 g propylene monomer, a polymerizationtemperature of 70° C. and a polymerization time of 67 minutes. Thecatalyst was prepared by combining 4 μmolrac-[1,2-ethanediylbis(1-indenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and 4 μmol [Me₂ NHPh]⁺ [B(C₆F₅)₄ ]⁻ in toluene. 164.8 g of crystalline polypropylene was obtained.

EXAMPLE 39

Preparation of Ethylene/Propylene Copolymer Polymerization usingrac-[1,2-ethanediylbis(1-tetrahydroindenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and B(C₆ F₅)₃

The general procedure was followed using 840 g mixed alkanes, 32 Δpsi(220 kPa) hydrogen, 75 g propylene monomer and ethylene monomer ondemand at 500 psig (3450 kPa) with a temperature of 130° C. and run timeof 15 minutes. The catalyst was prepared by combining 3 μmolrac-[1,2-ethanediylbis(1-tetrahydroindenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and 3 μmol B(C₆ F₅)₃ intoluene. 19.6 g of an ethylene/propylene copolymer was obtained.

EXAMPLE 40

Preparation of Isotactic Polypropylene usingrac-[1,2-ethanediylbis(1-(2-methyl-4-phenyl)indenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and B(C₆ F₅)₃ with Hydrogen

The general procedure was followed (except as noted below) using 723 gsolvent, 100 Δpsi (690 kPa) hydrogen, 201 g propylene monomer with atemperature of 70° C. and a polymerization time of 30 minutes. Thecatalyst was prepared by combining 2 μmolrac-[1,2-ethanediylbis(1-(2-methyl-4-phenyl)indenyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and 2 μmol B(C₆ F₅)₃ intoluene. The reactor bottom valve plugged and the contents of thereactor could not be emptied immediately after the polymerization. Thereactor was vented. The reactor was then pressurized with nitrogen gasto 400 psig (2.8 MPa) and vented. This was repeated two more times toremove the unreacted propylene monomer. The contents of the reactor werethen heated quickly to 160° C. and the contents removed as a solution.107.2 g of isotactic polypropylene was obtained (57 percent m pentad by¹³ C NMR analysis).

EXAMPLE 41

Preparation of Ethylene/Propylene Copolymer using[2,2-propanediyl(9-fluorenyl)(cyclopentadienyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and B(C₆ F₅)₃

The general procedure was followed using 719 g mixed alkanes, 25 Δpsi(170 kPa) hydrogen, 200 g propylene monomer and 26 g ethylene monomerwith a temperature of 70° C. and polymerization time of 30 minutes. Thecatalyst was prepared by combining 10 μmol[2,2-propanediyl(1-fluorenyl)(cyclopentadienyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and 10 μmol B(C₆ F₅)₃ intoluene. 69.4 g Of an ethylene/propylene amorphous copolymer wasobtained.

EXAMPLE 42

Preparation of Syndiotactic Polypropylene using[2,2-propanediyl(1-fluorenyl)(cyclopentadienyl)]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene) and methylalumoxane (MAO)

The general procedure was followed using 719 g mixed alkanes, 25 Δpsi(170 kPa) hydrogen, 200 g propylene monomer and 26 g ethylene monomerwith a temperature of 70° C. and run time of 30 minutes. The catalystwas prepared by combining 10 μmol [2,2-propanediyl(1-fluorenyl)(cyclopentadienyl)]zirconium (trans,trans-1,4-diphenyl-1,3-butadiene)and 10,000 μmol 10 percent percent MAO in toluene. 35.0 g Ofsyndiotactic polypropylene was obtained (74.7 percent r pentad by ¹³ CNMR analysis).

EXAMPLE 43

Preparation of Isotactic Polypropylene usingrac-[1,2-ethanediylbis(1-indenyl)]hafnium(trans,trans-1,4-diphenyl-1,3-butadiene) and B(C₆ F₅)₃

The general procedure was followed using 715 g mixed alkanes, 25 Δpsi(170 kPa) hydrogen, 200 g propylene monomer with a temperature of 70° C.and polymerization time of 60 minutes. The catalyst was prepared bycombining 5 μmol rac-[1,2-ethanediylbis(1-indenyl)]hafnium(trans,trans-1,4-diphenyl-1,3-butadiene) and 5 μmol B(C₆ F₅)₃ intoluene. 60.7 g Of isotactic polypropylene was obtained (83 percent mpentad by ¹³ C NMR analysis).

Gas Phase Reactor Description

Gas phase reactions were carried out in a 6-liter gas phase fluid bedreactor having a four inch diameter, thirty inch long, cylindricalfluidization zone and an eight inch diameter ten inch long velocityreduction zone which are connected by a transition section havingtapered walls. Monomers, hydrogen and nitrogen enter the bottom of thereactor where they pass through a gas distributor plate. The flow of gasis typically 2 to 8 times the minimum fluidization velocity of the solidparticles. Most of the suspended solids disengage in the velocityreduction zone. The reactant gases exit the top of the fluidization zoneand pass through a dust filter to remove any particulates. The gasesthen pass through a gas booster pump. No condensation of volatiles isemployed. The polymer is allowed to accumulate in the reactor over thecourse of the reaction. Polymer is removed from the reactor to arecovery vessel by opening a valve located at the bottom of thefluidization zone. The polymer recovery vessel is kept at a lowerpressure than the reactor.

EXAMPLE 44

Preparation Ethylene/1-butene Copolymer Under Gas Phase PolymerizationConditions

The catalyst was prepared by impregnating a toluene solution of 2 μmolrac-[1,2-ethanediylbis(1-indenyl)]zirconium(trans,trans-1,4-diphenylbutadiene) and 6 μmol B(C₆ F₅)₃ on 0.1 grams ofDavison™ 948 silica (available from Davison Chemical Company) which hadbeen treated with 1.0 gram of triethylaluminum/gram of silica. Thereactor was charged with 240 psi (1650 kPa) of ethylene, 5.4 psi (37kPa) of 1-butene, 1.3 psi (9 kPa) of hydrogen and 53 psi (370 kPa) ofnitrogen. The reactor temperature was set at 72° C. and the catalyst wasinjected. A 6° C. exotherm was recorded upon catalyst injection. Thetemperature returned to 74° C. within 3 minutes and the temperatureremained steady at 74° C. for the duration of the run. 14.3 g of afree-flowing polymer powder were recovered after 39 minutes operation.

EXAMPLE 45

Preparation Ethylene/Propylene Copolymer having Isotactic PropyleneSegments

The catalyst was prepared by impregnating a toluene solution of 2 μmolrac-[1,2-ethanediylbis(1-indenyl)]zirconium(trans,trans-1,4-diphenylbutadiene) and 6 μmol B(C₆ F₅)₃ on 0.1 grams ofDavison™ 948 silica (available from Davison Chemical Company) which hadbeen treated with 1.0 gram of triethylaluminum/gram of silica. Thereactor was charged with 95 psi (650 kPa) of propylene, about 3 psi (20kPa) of ethylene, 1.5 psi (10 kPa) of hydrogen and 42 psi (290 kPa) ofnitrogen. The reactor temperature was set at 70° C. and the catalyst wasinjected. The temperature remained steady at 70° C. for the duration ofthe polymerization. 4.6 g Of a free-flowing isotactic propylene/ethylenecopolymer powder were recovered after 60 minutes. (m pentad=71 percentby ¹³ C NMR analysis).

EXAMPLE 46

Preparation of rac-1,2-ethanediyl[bis-(1-indenyl)]zirconium(η⁴-1-phenyl-1,3-pentadiene)

In an inert atmosphere glove box 0.896 g (2.14 mmol) ofrac-1,2-ethanediyl[bis-(1-indenyl)]zirconium dichloride (in 50 ml oftoluene) were combined with 0.309 g of 1-phenyl-1,3-pentadiene (2.14mmol), followed by addition of 1.8 ml of nBuLi (4.5 mmol, in hexane).The color of the reaction quickly turned red. The reaction mixture wasstirred at about 25° C. for 30 minutes followed by heating at reflux fortwo hours, followed by continued stirring at about 25° C. for 18 hours.The product was collected by filtering, concentrating the filtrate toapproximately 30 ml, and cooling the filtrate to approximately -34° C.for about 18 hours. 0.225 g (21.4 Percent) of recrystallized product wasisolated as dark red microcrystals after decanting the mother liquor anddrying the product under reduced pressure. The product was identified by¹ H NMR spectrum as rac-1,2-ethanediyl[bis-(1-indenyl)]zirconium(η⁴-1-phenyl-1,3-pentadiene).

EXAMPLE 47

Batch Isotactic Polypropylene Polymerization Using rac-[bis-1,1'-(η⁵-indenyl)-1,2-ethanediyl]zirconium (η⁴ -1-phenyl-1,3-pentadiene) andB(C₆ F₅)₃ with Hydrogen

The general polymerization procedure was followed using 734 g solvent,26 Δpsi (180 kPa) hydrogen, 200 g propylene monomer with a reactiontemperature of 70° C. and run time of 30 minutes. The catalyst wasprepared by combining 4 μmol rac-[bis-1,1'-(η⁵-indenyl)-1,2-ethanediyl]zirconium (η⁴ -1-phenyl-1,3-pentadiene) and 4μmol B(C₆ F₅)₃ in toluene. 82 g of crystalline polypropylene wasobtained.

EXAMPLE 48

Batch Ethylene/Styrene Polymerization usingrac-[1,2-ethanediylbis-(1-indenyl)]zirconium (η⁴-s-trans-1,4-trans,trans-diphenyl-1,3-butadiene) and B(C₆ F₅)₃ withHydrogen

The general polymerization procedure was followed using 365 g solvent,51 Δpsi (350 kPa) hydrogen, 458 g styrene monomer with a temperature of70° C. and 200 psig (1.4 MPa) of ethylene on demand and a run time of 15minutes. The catalyst was prepared by combining 4 μmol ofrac-1,2-ethanediyl[bis-(1-indenyl)]zirconium (η⁴-s-trans-1,4-trans,trans-diphenyl-1,3-butadiene) and 4 μmol of B(C₆ F₅)₃in toluene. 19.8 g of an ethylene/styrene copolymer was isolated.

EXAMPLE 49

Batch Ethylene/1-Octene Polymerization usingrac-[1,2-ethanediylbis-(2-methyl-4-phenyl-1-indenyl)]zirconium (η⁴-s-trans-1,4-trans,trans-diphenyl-1,3-butadiene) and B(C₆ F₅)₃ withHydrogen

The general procedure was followed using 741 g solvent, 26 Δpsi (180kPa) hydrogen, 129 g 1-octene monomer with a temperature of 140° C. and500 psig (3.4 MPa) of ethylene on demand and run time of 15 minutes. Thecatalyst was prepared by combining 1 μmol ofrac-[1,2-ethanediylbis-(2-methyl-4-phenyl-1-indenyl)]zirconium (η⁴-s-trans-1,4-trans,trans-diphenyl-1,3-butadiene) and 1 μmol B(C₆ F₅)₃ intoluene. 13.1 g of an ethylene/1-octene copolymer was isolated.

What is claimed is:
 1. Compositions of matter useful as olefinpolymerization catalysts comprising:1) a metal complex containing twocyclopentadienyl groups or substituted cyclopentadienyl groups, saidcomplex corresponding to the formula:

    CpCp'MD

wherein: M is titanium, zirconium or hafnium in the +2 or +4 formaloxidation state; Cp and Cp' are each substituted or unsubstitutedcyclopentadienyl groups bound in an η⁵ bonding mode to the metal, saidsubstituted cyclopentadienyl group being substituted with from one tofive substituents independently selected from the group consisting ofhydrocarbyl, silyl, germyl, halo, cyano, hydrocarbyloxy, and mixturesthereof, said substituent having up to 20 nonhydrogen atoms, oroptionally, two such substituents (except cyano or halo) together causeCp or Cp' to have a fused ring structure, or wherein one substituent onCp and Cp' forms a linking moiety joining Cp and Cp'; D is a stable,conjugated diene, optionally substituted with one or more hydrocarbylgroups, silyl groups, hydrocarbylsilyl groups, silylhydrocarbyl groups,or mixtures thereof, said D having from 4 up to 40 nonhydrogen atoms andforming a π-complex with M when M is in the +2 formal oxidation state,and forming a σ-complex with M when M is in the +4 formal oxidationstate; 2) a cocatalyst or activating technique selected from the groupconsisting of:2a) Lewis acids selected from the group consisting ofC₁₋₃₀ hydrocarbyl substituted Group 13 compounds; halogenated C₁₋₃₀hydrocarbyl substituted Group 13 compounds; amine-, phosphine-,aliphatic alcohol-, and mercaptan- adducts of halogenated C₁₋₃₀hydrocarbyl substituted Group 13 compounds, and combinations thereof;2b) oxidizing salts corresponding to the formula:

    (Ox.sup.e+).sub.d (A.sup.d-).sub.e

wherein: Ox^(e+) is a cationic oxidizing agent having a charge of e+; eis 1 or 2; and A is a noncoordinating compatible anion having a chargeof d-; d is an integer from 1 to 3;2c) carbenium salts corresponding tothe formula:

    ©.sup.+ A.sup.-

wherein: ©⁺ is a C₁ -C₂₀ carbenium ion; and A⁻ is a noncoordinatingcompatible anion having a charge of -1;2d) an activating techniquecomprising electrolyzing the metal complex under bulk electrolysisconditions in the presence of an electrolyte of the general formula:

    G.sup.+ A.sup.-

wherein A- is a noncoordinating compatible anion having a charge of -1;and G+ is a cation which is non-reactive towards the metal complex andthe catalyst;2e) polymeric or oligomeric alumoxanes; 2f) salts of asilylium ion and a noncoordinating, compatible anion represented by theformula:

    R.sup.#.sub.3 Si(X.sup.#).sub.s.sup.+ A.sup.-

wherein: R^(#) is C₁₋₂₀ hydrocarbyl, s is 0 or 1, X^(#) is a neutralLewis base, and A⁻ is as previously defined; and2g) Bronsted acid saltshaving the formula:

    (L-H).sup.+.sub.d (A).sup.d-

wherein: L is a neutral Lewis base;(L-H)⁺ is the conjugate Bronsted acidof L; A is a noncoordinating compatible anion having a charge of d-; andd is an integer from 1 to 3;with the proviso that when the cocatalyst isa Bronsted acid salt of 2g), then: D is a terminally C₁₋₁₀ hydrocarbylsubstituted 1,3-butadiene π-bonded to the M; andM is titanium, zirconiumor hafnium in the +2 formal oxidation state.
 2. The composition ofmatter of claim 1 wherein the metal complex corresponds to the formula:##STR10## wherein: M is zirconium or hafnium, in the +2 or +4 formaloxidation state;R' and R" in each occurrence are independently selectedfrom the group consisting of hydrogen, hydrocarbyl, silyl, germyl,cyano, halo and combinations thereof, said R' and R" having up to 20non-hydrogen atoms each, or adjacent R' groups or adjacent R" groups(when R' and R" are not hydrogen, halo or cyano) together form adivalent derivative thereby forming a fused ring, or one R' and one R"together (when R' and R" groups are not hydrogen halo or cyano) combineto form a divalent radical linking the two substituted cyclopentadienylgroups; and D is as previously defined in claim
 1. 3. The composition ofclaim 1 wherein the metal complex is:a 1,2-ethanediyl(bis-,η⁵-indenyl)zirconium diene complex, a1,2-ethanediylbis(4-phenyl-1-indenyl)zirconium diene complex, a1,2-ethanediyl bis(2-methyl-4-phenyl-1-indenyl)zirconium diene complex,a 1,2-ethanediyl bis(4-naphthyl-1-indenyl)zirconium diene complex, a1,2-ethanediyl bis(2-methyl-4-naphthyl-1-indenyl)zirconium dienecomplex, a 1,2-ethanediyl bis(2-methyl-4,7-diphenyl-1-indenyl)zirconiumdiene complex, a 2,2-propanediyl bis(η⁵ -indenyl)zirconium dienecomplex, a 2-(cyclopentadienyl)-2-(9-fluorenyl)propanediylzirconiumdiene complex, a 2,2-propanediyl bis(4-phenyl-1-indenyl)zirconium dienecomplex, a 2,2-propanediyl bis(2-methyl-4-phenyl-1-indenyl)zirconiumdiene complex, a 2,2-propanediyl bis(4-naphthyl-1-indenyl)zirconiumdiene complex, a2,2-propanediylbis(2-methyl-4,7-diphenyl-1-indenyl)zirconium dienecomplex, a dimethylsilanediylbis(2-methyl-4-naphthyl-1-indenyl)zirconiumdiene complex, a dimethylsilanediylbis(η⁵ -indenyl)zirconium dienecomplex, a dimethylsilanediyl(cyclopentadienyl)(9-fluorenyl)zirconiumdiene complex, a dimethylsilanediyl bis(4-phenyl-1-indenyl)zirconiumdiene complex, a dimethylsilanediylbis(2-methyl-4-phenyl-1-indenyl)zirconium diene complex, adimethylsilanediyl bis(4-naphthyl-1-indenyl)zirconium diene complex, ora dimethylsilanediyl bis(2-methyl-4,7-diphenyl-1-indenyl)zirconium dienecomplex.
 4. The composition of claim 1 wherein the Lewis acid istris(pentafluorophenyl)borane.
 5. The composition of claim 4additionally comprising a polymeric or oligomeric alumoxane.
 6. Thecomposition of claim 1 additionally comprising hydrogen or ethylene. 7.The composition of claim 2, wherein M is zirconium or hafnium in the +2formal oxidation state and the diene is bound to the metal in aπ-complex structure.
 8. The composition of claim 7 wherein D is a1,3-butadiene that is terminally substituted with one or two C₁₋₁₀hydrocarbyl groups.
 9. The composition of claim 7, wherein the diene is1,4-diphenylbutadiene or 1,4-ditolylbutadiene.
 10. The composition ofclaim 7, 8 or 9 wherein the cocatalyst is tris(pentafluorophenyl)borane.11. The composition of claim 10, additionally comprising a polymeric oroligomeric alumoxane.
 12. The composition of claim 2, wherein M iszirconium or hafnium in the +4 formal oxidation state and the diene isbound to the metal in a σ-complex structure and is in the s-cisconfiguration.
 13. The composition of claim 12 wherein D is1,3-butadiene or a 1,3-butadiene substituted at the 2 or 3 position withone or two C₁₋₁₀ hydrocarbyl groups.
 14. The composition of claim 13,wherein the diene is isoprene or 2,3-dimethylbutadiene.
 15. Thecomposition of claim 12, 13, or 14, wherein the cocatalyst istris(pentafluorophenyl)borane.
 16. The composition of claim 15,additionally comprising a polymeric or oligomeric alumoxane.
 17. Thecomposition of claim 1 obtained by combining a diene complex with aBronsted acid salt wherein the diene complex has the formula: ##STR11##wherein: M' is zirconium or hafnium in the +2 formal oxidation state;R'and R" in each occurrence is independently selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R' and R" having up to 20 non-hydrogen atoms,or adjacent R' groups or adjacent R" groups (when R' and R" are nothydrogen, halo or cyano) together form a divalent derivative therebyforming a fused ring or where one R' and one R" combine to form adivalent radical linking the two cyclopentadienyl groups; D is a C₁₋₁₀hydrocarbyl substituted 1,3-butadiene which is π-bonded to the metal;and the Bronsted acid salt has the formula:

    (L-H).sup.+ (BQ'.sub.4).sup.-

wherein: L is a neutral Lewis base; (L-H)⁺ is the conjugate BronstedAcid of L; B is boron; Q' is a fluorinated C₁ to C₂₀ hydrocarbyl group.18. The composition of claim 17 wherein (BQ'₄)⁻ istetrakispentafluorophenyl borate, M' is zirconium or hafnium and thediene is 2,4-hexadiene, 1-phenyl-1,3-pentadiene, 1,4-diphenylbutadieneor 1,4-ditolylbutadiene.
 19. The composition of claim 1 wherein themetal complex is bis(η⁵ -cyclopentadienyl)zirconium s-trans(η⁴-1,4-trans, trans-diphenyl-1,3-butadiene),bis(cyclopentadienyl)zirconium s-cis(2,3-dimethyl-1,3-butadiene),dimethylsilanediyl-bis((2-methyl-4-phenyl)-1-indenyl)zirconiums-trans(η⁴ -1,4-trans-trans-diphenyl-1,3-butadiene),dimethylsilanediyl-bis((2-methyl-4-(1-naphthyl))-1-indenyl)zirconiums-trans(η⁴ -1,4-trans-trans-diphenyl-1,3-butadiene),1,2-ethanediyl-bis(2-methyl-4-(1-phenyl)-1-indenyl)zirconium s-trans(η⁴-1,4-trans-trans-diphenyl-1,3-butadiene),1,2-ethanediyl-bis(2-methyl-4-(1-napthyl)-1-indenyl)-zirconiums-trans(η⁴ -1,4-trans-trans-diphenyl-1,3-butadiene),[1,2-ethanediylbis(1-indenyl)]zirconium s-trans(η⁴-trans,trans-1,4-diphenyl-1,3-butadiene),[1,2-ethanediylbis(1-tetrahydroindenyl)]-zirconium s-trans(η⁴-trans,trans-1,4-diphenyl-1,3-butadiene),[1,2-ethanediylbis(1-indenyl)]hafnium s-trans(η⁴-trans,trans-1,4-diphenyl-1,3-butadiene), or[2,2-propanediyl(9-fluorenyl)-(cyclopentadienyl)]-zirconium(trans,trans-1,4-diphenyl-1,3-butadiene).
 20. The composition of claim 1wherein the metal complex has the formula: ##STR12## wherein: M istitanium, zirconium or hafnium in the +2 or +4 formal oxidation state;R'and R" in each occurrence are independently selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, or adjacent R' groups or adjacent R" groupstogether form a divalent derivative thereby forming a fused ring; E issilicon or carbon; x is an integer from 1 to 8; R'" is selected from thegroup consisting of hydrogen, methyl, benzyl, tert-butyl and phenyl; andD is a conjugated diene of 5 to 40 carbon atoms.
 21. The composition ofclaim 20 wherein the metal complex is an ansa rac-metal complex.